A steady state-fluorescence (SSF) technique for studying film formation from surfactant-free, slightly crosslinked polystyrene (PS) latex particles is reported. The powder films were prepared from fluorescein (F)-labeled PS particles at room temperature. The mechanically strong films were obtained by annealing these films at elevated temperatures in 5, 10, 20, and 30 min time intervals above the glass transition (T-g) temperature of polystyrene. Scattered light (I-s) and fluorescence (I-F) intensities from F were monitored after each annealing step to investigate the three different film formation stages called void closure, healing, and interdiffiusion. The evolution of transparency of the latex films was monitored by using a photon transmission technique. Scanning electron microscopy (SEM) was employed to detect the variation in physical structure of the annealed latex films. Onset temperature for void closure, T-m, and healing temperatures, T-h, were determined and corresponding activation energies were measured. Void closure and interdiffusion stages were also modeled and the related activation energies were also determined. It was observed that lower energy is needed for the void closure process than interdiffusion of chains across the particle-particle boundaries.