A family of amphiphilic graft copolymers were prepared from a maleated polypropylene (PP-g-MA) and various crystalline poly(oxyethylene)-segmented amines of 1000 to 3000 molecular weight. Structurally, these copolymers consist of polypropylene (PP) backbone and several crystalline poly(oxyethylene) (POE) pendants in the structure. In the observation of their phase behaviors by using a differential scanning calorimeter (DSC), the interference between the POE segments and PP backbone was found. In a particular case (PP-g-MA/ED-2001), the heat of POE crystallization did not show off in the cooling curve of the DSC, but appeared during the consecutive heating process. Generally, heating and cooling patterns of the DSC analyses showed the shifts of melting and crystallizing temperatures, depending on the length and the termini of POE, from those of the starting materials— PP-g-MA and POE amines. The TGA and optical microscopy observation further supported the DSC analyses.