Penny meets Raj and Wolowitz in the pilot episode of The Big Bang Theory. Wolowitz will begin his lifetime of sleazily hitting on her while Wolowitz is unable to talk to her.
Sheldon: I'll have a diet Coke. Penny: Can you please order a cocktail? I need to practice mixing drinks. Sheldon: Fine... I'll have a virgin Cuba Libre. Penny: That's... rum and Coke without the rum. Sheldon: Yes, and would you make it diet?