In this study, the high entropy/ceramic composite coating (AlCoCrFeNi)x/(WC–10Co)1-x (x = 100(W0), 75(W25), 50(W50)) were prepared on 3Cr13 stainless steel via high velocity oxy-fuel (HVOF) thermal spraying technology. The microstructure, phase composition, microhardness, nanoindentation, wear behavior and wear mechanism of the coatings were studied in detail. The results shown that the W0 coating had two phases (FCC + BCC), and the reinforced phase of composite coatings (W25 and W50) was WC phase. The average microhardness of the W0, W25 and W50 coatings were 558 HV0.3, 688 HV0.3 and 783 HV0.3. Nanoindentation test shown that the H/E and H3/E2 ratios of FCC and BCC phases increased with the addition of WC. Under the load condition of 30 N, the volume loss rate of W50 coating was only 1/10 of that of the W0 coating. The wear process of W0 coating were mainly affected by abrasive wear and adhesive wear, accompanied by fatigue wear and less oxidation wear. During the wear process, the second phase strengthening of WC in the composite coatings protected the adhesive layer from bulk spalling, and the wear resistance of the composite coatings were sharply improved. The wear mechanism of the composite coatings was also discussed in this work.