What I mean is if a Smeargle sketched a move on or off screen. If the answer is yes, what episode and what sketched move(s) has Smeargle used. I'd also like to know if a Smeargle sketched a move (on screen), but didn't use it.
Yes. It was used in Smashing with Sketch!, where Illima's Smeargle uses it to copy Jessie's Wobbuffet's Counter. It also copies Ikari's Mienshao's Drain Punch and High Jump Kick later on in the episode.
Hope I helped!
Yes In the episode Smashing with Sketch! Ilima's Smeargle used Sketch. This is how Bulbapedia describes it:
Smeargle grabs its tail and waves it around, causing the image of a pencil to circle around the opponent while leaving behind a trail of pink sparkles. Smeargle then learns the last move used by the opponent.
It apparently Sketched Counter.