Photochemical reactions are a powerful tool in (bio)materials design due to the spatial and temporal control light can provide. To extend their applications in biological setting, the use of low-energy, long wavelength light with high penetration propertiesis required. Further regulation of the photochemical process by additional stimuli, such as pH, will open the door for construction of highly regulated systems in nanotechnology- and biology-driven applications. Here we report the green light induced [2+2] cycloaddition of a halochromic system based on a styrylquinoxaline moiety, which allows for its photo-reactivity to be switched on and off by adjusting the pH of the system. Critically, the [2+2] photocycloaddition can be activated by green light (λ up to 550 nm), which is the longest wavelength employed to date in catalyst-free photocycloadditions in solution. Importantly, the pH-dependence of the photo-reactivity was mapped by constant photon action plots. The action plots further indicate that the choice of solvent strongly impacts the system’s photo-reactivity. Indeed, higher conversion and longer activation wavelengths were observed in water compared to acetonitrile under identical reaction conditions. The wider applicability of the system was demonstrated in the crosslinking of an 8-arm PEG to form hydrogels (ca. 1 cm in thickness) with a range of mechanical properties and pH responsiveness, highlighting the potential of the system in materials science.