Contrary to the widely accepted observation that grain-boundary amorphous films for a given Si3N4 composition have common (equilibrium) widths and compositions, a significant variation for both parameters from film to film was observed In an undoped high-purity Si3N4 prepared using a hot isostatic pressing method. This material previously has been reported to have an equilibrium film width of 0.6 nm, as measured using a high-resolution electron microscopy (HREM) method; this value is significantly different from that which is typical for other high-purity Si3N4 ceramics (1.0 rim). A total of four boundaries were analyzed, using spatially resolved electron energy-loss spectroscopy methods, which can give the chemical width and composition for the film. Widths of these grain-boundary films were substantially different from each other; only the thinnest matches the previous HREM observations. The nitrogen content in the film decreased concurrently as the film thickened. This material had many cavities and complicated configurations at triple pockets, because of the very low total-SiO2 content (0.55 vol%). They created locally different equilibrium conditions for grain-boundary films, in comparison with other fully densified Si3N4, causing such strong variation in both film structure and chemistry. This observation reveals the importance of triple pockets in equilibrium film structures, providing new insight in evaluating the absorption and wetting models. The thinnest film may correspond to the amorphous structure that is required to bind two randomly oriented Si3N4 grains under greater local stress.