In this study, we describe a novel strategy to design and construct POSS-modified silane layer on carbon fiber (CF) to strengthen the interfacial adhesion and anti-hydrothermal aging behaviors of CF-reinforced copoly(phthalazinone ether sulfone)s (PPBES). POSS was first modified by 3-aminopropyltriethoxysilane (APS) to improve chemical reactivity. Without separation and purification, APS-c-POSS was used to functionalize CF to improve reactivity and ensure the covalent linkages between CF and POSS-modified silane layer. CF coated with POSS-modified silane layer was obtained by in situ hydrolysis of APS-c-POSS. FTIR and XPS confirmed the chemical bonds between CF and POSS-modified silane layer. Dynamic contact angle, dynamic wetting test and AFM tests demonstrated that POSS-modified silane coating can increase the wettability and roughness, which could improve interlaminar shear strength and flexural strength of CF/PPBES composites by 17.5 and 30.0% with slight enhancement on tensile strength of CF. The failure mechanisms of CF/PPBES composites with and without POSS-modified silane layer were both investigated by SEM in detail. Moreover, this layer was helpful to dynamic mechanical property and hydrothermal resistance of CF/PPBES composites. This study provides alternate strategy to modify CF with POSS, which will significantly broaden the application field of POSS in advanced composites.