The multiple melting-peak behavior of polypropylene (PP) in nano-CaCO/PP composites and modified nano-CaCO/PP composites were investigated under the condition of isothermal crystallization and nonisothermal crystallization. The result indicated that the addition of nano-CaCO markedly increased the crystallization temperatures of PP and induced the formation of the β-crystal of PP. The crystallization temperatures of nano-CaCO/PP composites modified by reactive monomers were further increased, but the melting-peak intensity of the β-crystal of PP was not greatly influenced. While in the presence of dicumyl peroxide, nano-CaCO/PP composites modified by reactive monomers led to the significant increase in the melting-peak intensity of the β-crystal of PP. The double melting-peak of PP was observed, which was attributed to the formation of two kinds of different crystallization forms of α-crystal or β-crystal during the crystallization of PP. With the increase of crystallization temperatures, the double melting-peak moved toward the high-temperature side. The intensity of high-temperature melting peak was higher than that of low-temperature melting peak in nano-CaCO/PP composites. While in modified nano-CaCO/PP composites crystallized at higher temperature, the intensity of high-temperature melting peak was lower than that of low-temperature melting peak. The isothermal crystallization time had little effect on the melting temperatures.