A novel method to investigate the early formation stages of polycrystalline (Pb1-xCax)TiO3 (PCT) perovskite films by means of traditional Brillouin and micro-Brillouin spectroscopy (BS, mBS) is described in the present work. The films were prepared by chemical solution deposition (CSD) onto oxidized (100)Si substrates and treated at temperatures between 350-650 degrees C by rapid thermal processing (RTP). The elastic instability observed by Brillouin spectroscopy at the nano-structured state of the PCT films was used here to determine their crystallization temperatures. Coexistence of different nanocrystalline phases (e.g., pyrochlore, perovskite) in the films could also be detected by this technique. The reliability of these results is demonstrated by complementary information obtained by X-ray diffraction (XRD) and scanning force microscopy (SFM). The effects of the annealing temperature and of the Ca2+ content on the crystallization process of these films are also discussed.