Consequently, we can demonstrate intrinsic three-state photoswitching with reversible and quantitative access to all three states, corresponding modulation of thermal isomerization barriers, and triggered energy release. No acid addition is necessary for multi-state controllability. Additionally, our second generation aza-diarylethene 1 can be applied as potent light-controlled trigger for radical polymerization showing an up to 240% increase of polymerization speed compared to our first generation aza-diarylethene.