Organic crystals can respond dynamically to external stimuli such as light or heat, exhibiting bending, curling, hopping, and fracturing. These photodynamic crystals convert light into mechanical energy, offering potential applications in actuation, energy harvesting, flexible electronics, switchable reflectors, and sensing. Irradiation of crystalline azido compounds induces N₂ release, which drives such photomechanical responses. We show that photodynamic crystal fracture can enhance the efficiency of solid-state photoreactions by continually exposing fresh reactive surfaces. Although solid-state photochemistry is valued for its spatial and temporal control, it is often restricted by surfaceconfined reactivity, where passivating photoproduct layers limit bulk conversion. This limitation can be overcome through photofracking—photoinduced crystal disintegration— where cracking and fracturing expose new surfaces and extend the photoreaction toward higher conversion. In contrast, azido crystals engineered to pack into two-dimensional lattices exhibit restricted surface reactivity, making them promising for photolithographic applications. Confocal Raman microscopy, along with digital, SEM, and AFM imaging, confirmed that these crystals react only at the surface, and the resulting photoproducts can be harnessed for crystal patterning. Laser flash photolysis, ESR spectroscopy, and matrix isolation studies were used to elucidate the underlying photochemical mechanism of the azido compounds in both solution and the solid state. Overall, the factors governing whether azido crystals exhibit photodynamic behavior are discussed, linking fundamental photochemistry with emerging applications in materials science.