In order to effectively utilize recycled glass fiber, two polyvinylpyrrolidone water-based hybrid coatings were synthesized under acid catalysis and without adding catalyst using ethyl orthosilicate and coupling agent as precursors and polyvinylpyrrolidone as film-forming agent. The recycled glass fibers were sized separately using the prepared hybrid coatings. The results showed that the surface roughness of the recycled glass fibers after the sizing treatment of the hybrid coatings prepared under acid-catalyzed conditions was greater compared with that of the hybrid coatings prepared under the condition of no added catalyst; The single-fiber tensile strengths of the recycled glass fibers after sizing treatment of the hybrid coatings prepared under acid-catalyzed conditions and conditions without added catalysts were 1322.7 ± 98.5 MPa and 1093.8 ± 53.8 MPa, which were increased by 39.8% and 15.6%, compared with the single-fiber tensile strengths of the recycled glass fibers. The use of single fiber fragmentation method to evaluate the interfacial properties of recycled glass fiber and epoxy resin shows that single fiber epoxy resin composite materials prepared from recycled glass fiber after sizing with hybrid coating prepared under acid catalytic conditions and without adding catalytic conditions The interfacial shear strengths are 53.5 MPa and 35.7 MPa respectively, which are 200.5% and 100.8% higher than the interfacial shear strengths of single fiber epoxy resin composites of recycled glass fibers without sizing treatment. Aqueous hybrid coatings prepared under acid-catalyzed conditions are shown to be feasible for recycling glass fibers.