Synthetic cellulose prepared by enzyme has the advantages of easy functionalization, easy preparation, and biocompatibility, making it an ideal material for constructing hydrophilic coating with functionalities. In this study, β-D glucose with phenolic group (arbutin) as a primer reacted with glucose 1-phosphate (G1P) under the catalysis of Clostridium thermocellum (CtCDP) to synthesize antibacterial cellooligomer. Then, the synthetic cellooligomer was dissolved into a homogeneous organic solution to prepare a functional hydrophilic coating composed of cellulose molecular chains on the surface of polyvinylidene fluoride (PVDF) membranes. The molecular structure of enzymatic antibacterial cellooligomer was characterized by fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). ATR-FTIR confirmed the successful preparation of cellulose coatings. The performance test results showed that the strong interaction at the interface between cellooligomer and PVDF membrane promoted the uniform distribution of cellulose molecules on the membrane surface, which greatly improved the hydrophilicity of PVDF membrane and enhanced the stability of the coating bonded to the substrate. Moreover, the cellulose molecular coating had excellent antifouling performance, outstanding antibacterial activity, and anti-adhesion to Staphylococcus aureus (S. aureus). This work provides a versatile platform for the time-saving and cost-effective fabrication of antifouling and antibacterial membranes.