Natalie Valentine's only appearance was in the episode "Green with N.V." She is the creator of the cologne Possession. Because of teenage rejection she loathed romance, calling the spies "16 year old popularity queens".
She was responsible of putting all men including Jerry Lewis are being hypnotized to find their true love by spraying the cologne Possession she had made. The girls were sent to investigate the incidents happened to their boyfriends and husbands' hypnotism. The girls went to the store where Natalie's perfumes have been sold and the clerk tells them that the perfumes are sold out before the Valentine's Day comes up. The clerk finally shows them the returning bottles and she tells them that she was one of the victims that her boyfriend went missing because of the perfume that she sprayed. Sam gets the sample of the Possession bottle and Alex put the drop of the liquid perfume to send to Jerry for analysis. Either of the 3 are secretly calls David for tonight's dance during their missions as it revealed that he was not on the canteen and the girls were unaware that they only send a voice message from his phone table.
The girls are now going to France and investigate the warehouse while spying on the roof and to find out that all hypnotized men got sprayed from her perfume are going inside the warehouse and the smell of her perfume was bad as they mentioned. The girls begin to take action until they were halted by hypnotized guards and ends up rejected. The girls then disguises themselves as men as they managed to enter the warehouse and they discovered all hypnotized men were working on Natalie's perfume and most of the pipe are dropping the scent of cologne as Clover smells at Alex. They saw the machine that mixes ingredients for her perfume as they check it out.
They investigate the machine called the "Possession Perspirator" and Sam calls Jerry and she found out that he's gone off in his office (being hypnotized from the sample they gave him.) Therefore, Natalie arrives at her warehouse in her business suit and the girls noticed her arrival as the hypnotized workers are throwing flower petals from the baskets toward her chanting "Found, true love..." as she walks straight to her warehouse.The girls hides from Natalie while the hypnotized workers continued throwing flower petals on Natalie and they pretend as hypnotized workers. Natalie goes inside the machine as it activates the heat procedure in the "Possession Perspitator" to make her completely sweat much to the girls discomfort on her actions and her sweat drops within the mix ingredients of the cologne to make the guys being possessed by the smell of perfume. However, Alex blew their disguises as she comments to Natalie "As if..?" making Natalie replied to them "What did you say?" She discovers their disguise as she removes Alex's mustache and orders her men to get them. The girls attempts to escape but failed as her men are formed as warehouse doors making Clover pulled up the snowboard gadget causes them to get crashed and face Natalie who wanted to be captured by them.
The girls are now in a cage along with the mix ingredients from her machine, Sam wants to talk about the mess she had made and Natalie calls the girls as "16 year old popularity queens were score some boys to chasing after them." She then tells them about her motives since New York City was only the beginning for her to make the cologne works for men to possessively in love with her. She's going to spray the entire male population with her scent of the perfume that she made and never worries about rejection. She then orders her men to drown the girls from her cage with the machine. With the girls' being dismayed wanted to be saved by Jerry as his jet arrives, he too was hypnotized by the perfume that they give the sample earlier and grabbing Natalie's leg and telling him to deal the girls.
Jerry then activates the machine to drown the girls and he goes with Natalie and she flies away with her plane. Sam then uses the Expandable Cable Bungee Belt to stick on the WOOHP jet's tail making them escape from drowning. Alex was impressed from her geniuses and Sam finally realizes how to negate Natalie's scent by using their own scents. They use their sweats on the mixed ingredients on the perfume while they were inside the machine. Sam managed to spray the guard when he caught them. Later in the sky, the girls finally prepare in their catsuits and take a jump to the planes and the captain and his crew are being sprayed by the girls. Natalie discovers the change of plans and using Jerry to pursue and attack the girls. Therefore, the girls managed to get in Natalie's plane as they use the Expandable Cable Bungee Belts to enter as Jerry overtakes the plane. Therefore, Clover finally put the cover using the wipe gadget and Sam managed to put a spray gadget on the plane's fans and they jumped in the sky causes Natalie's plane to be crashed in the ocean
At sunset, Jerry and Natalie are drenched in the ocean waters as they crashed on the beach. Jerry wakes up finally returns to normal and finally arrests Natalie for her crimes. After her arrest, Clover pointed out that Natalie had failed to properly use her beauty when younger and she replies that she didn't think about all these things nodding at Clover's beauty streak and she was finally taken in custody while sending her to the WOOHP helicopter.
- Natalie Valentine is similar to Violet Vanderfleet in motive, however Violet got rejected frequently where as Natalie never had a date.
- Natalie's name is a parody on Valentine's Day.