We explore a cross-linked polymer network based on a visible light photodynamic [2 + 2] cycloaddition driven by styrylpyrene chemistry. Based on a polymer backbone with pendent styrylpyrene units, the network can be formed by using λ = 450 nm irradiation. Upon irradiation with λ = 340 nm, a photostationary state is generated within the network with ∼17% of the styrylpyrene units open compared to close to 2% in the visible light cured state. The limited fraction of open [2 + 2] couples is caused by their proximity and is in sharp contrast to solution experiments on the photoreactive moiety. Thus, the polymer network retains its mechanical properties even at the photostationary point. We hypothesize that the application of an additional stimulus could serve as a second gate for inducing network disintegration by spacing the [2 + 2] units during ultraviolet irradiation.