The structural transformation of homogeneously nucleated metastable mesophase of polypropylene (PP) particles was investigated in this study. We demonstrated the formation of heterogeneity-free mesophase by slow cooling of the droplets unlike mesophase formation by quenching of the PP melt, which contained large number of bulk nuclei. Submicron size PP droplets were produced by thermal break up of PP and polystyrene layered film assembly. When cooled from melt, the PP droplets crystallized into mesophase at 44 degrees C revealing granular morphology. Subsequent heating thermogram of the PP particles showed a broad exotherm, which was attributed to the transformation of mesophase into alpha-phase. This transformation was investigated during heating by annealing the PP particles at different temperatures. Annealed PP particles were analyzed by means of thermal, morphological and structural properties measurements. Results revealed a two step process for the transformation process. In the first step, the internal rearrangement of PP chains, as against melting and recrystallization of the mesophase, was observed. Since granular morphology was not affected significantly up to 120 degrees C, it was suggested that translational and rotational motions of PP helices produced ordered a-phase. In the second step, increment in grain size distribution was observed, when the droplets were annealed at 140 degrees C. The results were attributed to enhanced chain mobility and merging of the grain boundaries. Annealing at 160 degrees C revealed the formation of short lamellar structures. Crystal thickening, melting and recrystallization of alpha-phase were suggested at high temperature annealing. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1672-1682, 2011