Serena is reading Nylon magazine with Scarlett Johansson on the cover, at that time Scarlett was engaged to her subsequent husband Ryan Reynolds. In real life Blake Lively married Ryan Reynolds after Scarlett and he divorced.
In this episode, Chuck talks about Marcus' people (meaning the English) being all about civility. In actuality Ed Westwick is English, while Patrick Heusinger is American.
With the exception of the pilot, all the episode titles were inspired by books or movie titles. The title here is a reference to the movie 'Never Been Kissed'