In this talk, we describe a novel orthogonal polymer semiconductor (OPS) that is capable of showing chemical and mechanical tolerance during multiple solution coating and photolithography processes. The critical step in a sol-gel reaction is the formation of a highly cross-linked network out of molecular precursors through hydrolysis and condensation reactions. By carefully manipulating this step, we could prepare self-assembled structures of either quasi-3D random or ladder characteristics. The resulting structures yielded films that are highly tolerant against harsh external stimuli. Consequently, we could demonstrate that sub-micron patterning and forming of tandem structures of OPS can be done readily through conventional photolithography with sequential solution and etching processes, and finally fabricate tandem electronic devices including a pn-complimentary inverter logic and pixelated polymer light-emitting diodes.