The electrical characteristics of complex films composed of poly(ethylene oxide) (PEO) and urea as a function of the urea concentration were examined in this study. Moreover, their structural characteristics were also compared. Depending on the urea concentration, the structural phases were classified as PEO+${eta}$-phase composite, ${eta}$-phase+${alpha}$-phase composites, or ${alpha}$-phase composite+urea. At urea concentrations below ~0.064 M, the ${eta}$-phase was dominant in the complex film. Moreover, the conductance increased rapidly with an increase in the urea concentration. For urea concentrations ranging from ~0.064 to ~0.25 M, the ${eta}$-phase was gradually substituted by the ${alpha}$-phase. As the film was composed entirely of the ${alpha}$-phase at urea concentrations greater than ~0.25 M, its conductance was decreased. In this study, the electrical characteristics observed for the different phases are analyzed and discussed.