To imitate the composition of natural bone and further improve the biological property of the materials, ZnO/hydroxyapatite/chitosan-polyethylene oxide@gelatin (ZnO/HAP/CS-PEO@GEL) composite scaffolds were developed. The core-shell structured chitosan-polyethylene oxide@gelatin (CS-PEO@GEL) nanofibers which could form the intramolecular hydrogen bond and achieve an Arg-Gly-Asp (RGD) polymer were first prepared by coaxial electrospinning to mimic the extracellular matrix. To further enhance biological activity, hydroxyapatite (HAP) was grown on the surface of the CS-PEO@GEL nanofibers using chemical deposition and ZnO particles were then evenly distributed on the surface of the above composite materials using RF magnetron sputtering. The SEM results showed that chemical deposition and magnetron sputtering did not destroy the three-dimensional architecture of materials, which was beneficial to cell growth. The cell compatibility and proliferation of MG-63 cells on ZnO/HAP/CS-PEO@GEL composite scaffolds were superior to those on CS-PEO@GEL and HAP/CS-PEO@GEL composite scaffolds. An appropriate amount of ZnO sputtering could promote the adhesion of cells on the composite nanofibers. The structure of bone tissue could be better simulated both in composition and in the microenvironment, which provided a suitable environment for cell growth and promoted the proliferation of MG-63 cells. The biomimetic ZnO/HAP/CS-PEO@GEL composite scaffolds were promising materials for bone tissue engineering.