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This invention provides a method, replica film, and application for directly detecting silicon nitride grain boundary phases. The method includes the following steps: S1, etching a polished silicon nitride ceramic sample with hydrofluoric acid solution; S2, replicating the etched polished surface with a first solvent and a cellulose acetate film to obtain a primary replica; S3, vacuum-depositing a carbon film onto the primary replica to obtain a secondary replica; S4, cutting and attaching the secondary replica film to low-temperature paraffin wax, then dissolving the cellulose acetate in a second solvent; S5, transferring the dissolved secondary replica film to a third solvent, and after the secondary replica film has fully expanded, retrieving it with a copper mesh, drying it, and observing it under an electron microscope. The method provided by this invention can separate the grain boundary phase from the silicon nitride main phase, obtaining the solid grain boundary phase while retaining the morphological outline of the silicon nitride main phase. This method is simple to operate, low in cost, and provides great convenience for studying the influence of grain boundary phases on the mechanical and optical properties of silicon nitride separately.