Polyelectrolyte complex films were prepared with two compounds, chitosan and poly(ethylene glycol)-monosuccinate, using a casting in order to synthesize a polyelectrolyte complex film with various mole ratios of chitosan and poly(ethylene glycol)-monosuccinate. The solution properties of isolated PEC were investigated for the effects of FTIR, pH value, Brookfield viscosity and cell viability assay using MTT staining. The PEC films were evaluated for mechanical properties by typical stress-strain curve, far thermal properties by DSC and TGA and for surface morphology Properties by SEM. Furthermore, the surface resistance, moisture regain and water content of the films were characterized. The solution properties were affected by several factors including the chitosan content in the PEC, the mixing ratio of PEG and chitosan, and pH. Several PEC in acidic conditions exhibited film formation under appropriate conditions of mixing ratio and chitosan concentration in the mixing process. These PEC films were found to have sufficiently flexible and stable properties due to their hydrophilic structure, which was farmed by the oppositely charged interaction between PEG-MS and chitosan matrix. The results showed the potential applicability of chitosan and poly(ethylene glycol)-monosuccinate films as a biocompatible polymer.