Collagen (COL) is a kind of natural polymer from animal biomass, which is rich in source, easy in processing and modification and degradable. Among collagen materials, sponges based on lyophilization have natural porosity, which not only provide sufficient space for oil phase storage, but also provide skeleton network for the fixation of functional micro-nano components. Using collagen sponge as framework, polydimethylsiloxane (PDMS) as hydrophobic modifier, and rutile-type titanium dioxide nanoparticles (TiO2) as photocatalyst, a multi-functional composite collagen sponge TiO2/PDMS-COL integrating of hydrophobicity, photocatalytic and sunlight-responsive antibacterial activity was fabricated. The morphology of TiO2/PDMS-COL was observed by FE-SEM, and the structure of TiO2/PDMS-COL was characterized by FT-IR, XPS, XRD and TG. The results confirm that TiO2 and PDMS are successfully compounded with COL. The adsorption capacity of the composite sponge toward CHCl3 is as high as 134 g/g. The contact angle is not decreased obviously after 20 cycles. The compound sponge shows a good separation ability for emulsion. Under the irradiation of sunlight, the degradation rate toward RhB reaches 88% within 80 min, and it is not decreased significantly after three cycles. Reactive oxygen species produced by TiO2 under sunlight endow the composite sponge with excellent sunlight-responsive antibacterial activity, that is, the antibacterial rates toward E. coli and S. aureus are more than 90%, respectively.