The effect of physicochemical properties of solvents on the microstructure of polyvinyl carbazole (PVK) film for non-volatile polymer memory was investigated. For the solubilization of PVK molecules and the preparation of PVK films, four solvents with different physicochemical properties of the Hildebrand solubility parameter and vapor pressure were considered: chloroform, tetrahydrofuran (THF), 1,1,2,2-tetrachloroethane (TCE), and N,N-dimehtylformamide (DMF). The solubility of PVK molecules in the solvents was observed by ultravioletvisible spectroscopy. PVK molecules were observed to be more soluble in chloroform, with a low Hildebrand solubility parameter, than solvents with higher values. The aggregated size and micro-/nano-topographical properties of PVK films were characterized using optical and atomic force microscopes. The PVK film cast from chloroform exhibited enhanced surface roughness compared to that from TCE and DMF. It was also confirmed that the microstructure of PVK film has an effect on the performance of non-volatile polymer memory.