The main purposes were evaluating the influence of different starches on the miscibility with Poly(ethylene oxide) (PEO) and their effects on the spherulite growth rate. Polymer-polymer miscibility in PEO/cationic starch and PEO/hydrophobic starch blends consisting of different w/w ratios (100/0, 95/05, 90/10, 80/20, 70/30, 65/35 and 60/40) was investigated. This analysis was based on the depression in the equilibrium melting temperature (T m 0). By treating the data of thermal analysis (Differential Scanning Calorimetry - DSC) with Nishi-Wang equation, a positive value (0.68) was found for the interaction parameter of PEO/cationic starch. For PEO/hydrophobic starch blends, a negative value (-0.63) was obtained for the interaction parameter. The results suggested that PEO/cationic starch system should be immiscible. However, the system PEO/hydrophobic starch was considered to be miscible in the whole range of studied compositions. 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