In this work, we developed a novel amphiphilic coating by incorporating poly (N-vinylpyrrolidone) (PVP), a highly hydrophilic polymer with strong physicochemically stability, into polydimethylsiloxane (PDMS) matrix. PVP was firstly functionalized with triethoxysilane and then directly crosslinked with PDMS to form an amphiphilic network coating at room temperature. Results suggested that the hydrophilicity of PDMS matrix was significantly improved after the modification. Moreover, compared to pristine PDMS, PDMS-PVP coatings could efficiently prevent the adhesion of bacteria and Navicula diatoms (both 99% reduction), as well as resist the attachment of mimetic barnacle (82% reduction). More importantly, PDMS-PVP coatings also showed excellent anti-biofouling performance for at least 4 months in the marine field tests. This work provides a novel strategy to prepare high-performance anti-biofouling coatings, which are expected to advance the development of environmentally-friendly coatings in marine applications.