Collagen fiber has attracted much attention due to its good biocompatibility and biodegradability. In the present research, we prepared a type of non-fluorine hydrophobic and oil-resistant material using collagen fiber, chitosan, and polydimethylsiloxane (PDMS) as raw materials. To improve oil/grease resistance, the first layer filled the porous matrix and was made from the cross-linking product of collagen fiber/chitosan and glutaraldehyde. This was followed by a simple coating of PDMS, to increase hydrophobicity and water resistance. Notably, 10 g/m2 of cross-linking product and 6 g/m2 of PDMS had a low pore size as well as a smooth and uniform surface, which made the composites exhibit excellent hydrophobic and oil-resistant properties (water contact angles of 141°), water and oil resistance (kit rating value of 12/12) and mechanical properties. Fluorine-free environment-friendly materials with high water and oil resistance play an important role in promoting the development of high-performance materials for food packaging.