This article discusses the phase separation and morphology of ethylcellulose/cellulose acetate phthalate blended films cast from methanol/methylene chloride (50/50 v/v) solvent mixture. The solvent system has been shown to be a cosolvent for CAP and a solvent/nonsolvent for EC. The two polymers have been shown to phase separate for all blend compositions via nucleation and growth. The morphology of these systems consists of a dispersion of broad size distribution of the minor component in a matrix of the major one. The formation of two layers due to coalescence of the dispersed phases and their eventual precipitation has been observed for the middle blend compositions. Finally, the phase separation in this system is discussed in terms of the Flory–Huggins theory and changes in the solvency mechanism during film casting. Enrichment of the solvent system in methanol at relatively early stages of film casting leads to changes in the system viscosity, relative chain conformation in solution, and chain diffusion. The effect of these parameters on the final morphology are discussed in terms of deviations from the equilibrium binodal decomposition.