To enhance the comprehensive performance of solid oxide fuel cells (SOFCs) ferritic stainless steel (FSS) interconnectors, a novel approach involving composite electrodeposition and thermal conversion is proposed to prepare Ni-doped Co-Mn composite spinel protective coatings on FSS surfaces. The process involves the composite electrodeposition of a Ni-doped Co-Mn precursor coating, followed by thermal conversion to obtain the Co-Mn-Ni composite spinel coating. Crofer 22H was used as the substrate and orthogonal experiments were designed to investigate the influences of deposition solution pH, stirring rate, cathode current density, and the element content of Mn and Ni on the surface morphology and properties of the composite coatings, respectively. The characterization of the prepared coatings was conducted through macroscopic and microscopic morphology observations of the component surface, energy dispersive spectroscopy (EDS) analysis, and area specific resistance (ASR) testing, etc. Finally, the optimized composite electrodeposition parameters and the Mn-Ni content ratio in the solution were obtained. Experimental results indicated that the composite spinel coating prepared with the optimized process parameters exhibited excellent adhesion to the substrate, and the diffusion and migration of Cr element has been effectively inhibited. Compared with the substrate, the ASR of the coated components has also been decreased simultaneously, which provided an effective method for the surface modification of SOFC FSS interconnectors.