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So If I want to say, for example
In this episode of the famous cartoon",
and seeing that "cartoon" is masculine in French, do I say
Dans cet épisode du célèbre dessin animé
OR
Dans cet épisode de le célèbre dessin animé.
I mean seeing that I'm using "de" as "of" and "le" as "the" and not for unspecified singular quantity, does the rule de+le=du still apply?
Yes. You must use "du" there. The only case where you may write "de le" is if it’s followed by a infinitive verb. Like in « Impossible de le voir » → "Impossible to see it/him".
