Warning! Spoilers ahead for Catwoman #30!
The Riddler might claim he started doing drugs to amplify his alertness and focus, but based on his past dealings with Harley Quinn, it's highly probable that he felt compelled to juice up because she outsmarted him and he needed to up his A-game.
Catwoman recently found the villain so hopped up on enhanced amphetamines that he almost didn't survive a night of chemical detoxing, as revealed in Catwoman #30 by Ram V., Fernando Blanco, Jordie Bellaire, Jordie Bellaire, and Tom Napolitano. The Riddler's addiction had become so overwhelming that he actually went on the prowl for more, which almost resulted in his own assassination had Catwoman not intervened.
When exactly Riddler first succumbed to drugs is unclear, but, in Catwoman #25, Selina knew he was already using during a temporary job alongside him and Penguin, meaning that something must have happened to him earlier on that compelled him to abuse drugs. But what could it have been? All signs now point to Harley Quinn & the Birds of Prey #3, which saw the Riddler try running over Harley with his truck to cash out on Joker's highly lucrative hit.
To keep Riddler from getting his bounty (and killing her), Harley engages in a battle of wits against the villain with her own riddle: "What's tiny in stature, but capable a' supportin' the weight of a whole house?" Angered that Harley would dare steal his own schtick and use it against him, Riddler goes on a verbal tirade about the indecency of it all, granting Harley enough time to render him incapable of driving (and running her over) by shooting him in the arm with a nail gun. In essence, she out-riddled the Riddler.
Understanding how the Riddler thinks is imperative to fully grasp the many ways in which this could affect him. The Riddler's entire identity is predicated on his mental prowess and ability to outsmart his victims, so anything that challenges this truth is detrimental to his wellbeing. Batman is essentially the only one of his foes whom Riddler perceives as his greatest opponent, and so losing to the Dark Knight is, while unfortunate, not the end of the world and just compels him to try harder.
But anyone else who encroaches on this territory is inconceivable. Riddler's inability to deal with competition is made apparent during "The Joker War," when losing a mere game of chess against Scarecrow causes Riddler to explode in a fit of rage. If losing a measly board game can throw Riddler out of wack, just imagine what the impact would be if he got outsmarted by, not a competitor, but a victim using his own method against him? It's enough to get him to resort to drugs, that's for sure.
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