Steady state fluorescence (SSF) and photon transmission (PT) techniques were used for studying film formation from TiO2 and Al2O3 covered polystyrene (PS) latex particles. These films were annealed at elevated temperatures in 10 min time intervals above glass transition (T-g) temperature of polystyrene. Fluorescence emission, I-P and transmitted photon, I-tr intensities were measured after each annealing step to monitor the stages of film formation. Films present dramatic increase in both I-tr and I-P above the certain onset temperature called minimum film forming temperature, T-0. Dissolution of annealed PS film, with high TiO2 content presented a nice, ordered nano-sized ceramic structure, which may predict the construction of nano-layer photonic crystals. It was observed that latex particles are encapsulated above a critical Al2O3 content of 33 wt% which corresponds to the critical occupation probability of p(c)=0.33 at which the film obey the site-percolation model with a critical exponent of 0.45.