>>29083164First, it eats status. Did you just set up a Sub on your sweeper as the enemy swapped in Sableye? No Prankster wisp for Sabbleye.
Second, it is fantastic for scouting. Did you just switch in your Mega-Gross on Clefable? Rather than waste a turn using Meteor Mash on the thing it switches in, use Substitute! You now get one free turn to choose the correct move for what switched in, as well as figure out what the enemy would pick to KO Megagross with this new mon, possibly even locking it in if you know it might have a choice item.
Third, rack up ticks. If you press Substitute, your enemy just took another round of Toxic/Burn damage. This could have just lowered it into KO range for your next attack.
Fourth, in general it is a very good move for calling bluffs. If someone switches in something weird on your Pokemon, you could pop a Sub just to check what they have planned without risking your 'mon or being in a good position if it tries to set up or status you.
Fifth, Mimkyu never dies in one hit, except to infiltrator/multi-hit mons, and basically gets a free Air Balloon but for status instead every time it switches in.