Crystallization of isotactic polypropylene (iPP) at the interface with crystalline films of two commercially employed nucleating agents (sodium benzoate (NaBz) and sodium 2,2’-methylene bis-(4,6-di-tert-butylphenyl)phosphate (NA-11)) and with a glass fiber (GF) was investigated using a polarized optical microscope. The analysis of the light intensity evolution during the crystallization process enabled the successful estimation of the time at which the crystal growth began, i.e., the induction time (ti), at various crystallization temperatures. Meaningful differences in the ti values were observed between the investigated systems. Moreover, the ti data have been analyzed according to different nucleation models proposed in the literature, which consider either the time to form the first crystalline layer in contact with the substrate or the time required to grow a cluster of critical size. It has been found that the two models are applicable in different temperature ranges depending on the efficiency of the given substrate. Therefore, in order to obtain the value of the surface free energy difference function, Δσ, which is directly related to the nucleation energy barrier and useful for the definition of a universal nucleating efficiency scale, a model that considers both the above-mentioned times was fitted to the overall data. The values of Δσ for the nucleation of iPP on the surface of the different substrates are thus obtained and discussed in the framework of the literature results.