The present work provides a comparative study on the photopatterning of epoxy-based thermosets as a function of network structure and network mobility. Local switching of solubility properties by light of a defined wavelength is achieved by exploiting versatile o-nitrobenzyl ester (o-NBE) chemistry. o-NBE derivatives with terminal epoxy groups are synthetized and thermally cured with different types of cycloaliphatic anhydrides via nucleophilic ring opening reaction. By varying the structure of the anhydride, glass transition temperature (Tg) and surface hardness are adjusted over a broad range. Once the network has been formed, the photolysis of the o-NBE groups enables a well-defined degradation of the 3D network. Fourier transform infrared (FT-IR) spectroscopy studies demonstrate that cleavage rate and cleavage yield increase with rising mobility of the network, which is either facilitated by inherent network properties (Tg below room temperature) or a simultaneous heating of the thermosets above their Tg. The formation of soluble species is evidenced by sol-gel analysis, revealing that low-Tg networks are prone to secondary photoreactions at higher exposure doses, which lead to a re-crosslinking of the cleaved polymer chains. The change in solubility properties is exploited to inscribe positive tone micropatterns within the thermosets by photolithographic techniques. Contrast curves show that the resist performance of rigid networks is superior to flexible ones, with a contrast of 1.17 and a resolution of 8 μm.