In order to further improve the mechanical properties of the CX stainless steel, CX steel powders were surface modified via the nano-WC particles using the electrostatic self-assembly method first. Then, the nano-WC reinforced CX steel samples were fabricated via selective laser melting (SLM) technology. The microstructure characteristics, elements distribution and mechanical properties were compared between the SLM nano-WC/CX steel samples and SLM CX steel samples via a series of advanced material characterization methods including optical microscope (OM), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), electron backscatter diffraction (EBSD) and etc. The results showed that the addition of 5vol.% nano-WC promotes the hardness of the SLM nano-WC/CX steel to increase from 352±8.2 HV0.2 to 361±23.5 HV0.2. Although its elongation has been reduced, the ultimate tensile strength (UTS) has been increased from 1091.4±6.12 MPa to 1109.7±15.26 MPa. In short, after the preliminary explorations, it can be found that the nano-WC modified CX steel powders fabricated through the electrostatic self-assembly means can effectively enhance the mechanical properties of the SLM CX steel samples.