With the rapid development of electronic technology and large-scale integrated circuit devices, it is very important to develop thermal management materials with high thermal conductivity. Silicon carbide whisker-reinforced copper matrix (Cu/SiCw) composites are considered to be one of the best candidates for future electronic device radiators. However, at present, most of these materials are produced by high-temperature and high-pressure processes, which are expensive and prone to interfacial reactions. To explore the plating solution system suitable for SiCw and Cu composite electroplating, we tried two different Cu-based plating solutions, namely a Systek UVF 100 plating solution of the copper sulfate (CuSO4) system and a Through Silicon Via (TSV) plating solution of the copper methanesulfonate (Cu(CH3SO3)2) system. In this paper, Cu/SiCw composites were prepared by composite electrodeposition. The morphology of the coating under two different plating liquid systems was compared, and the mechanism of formation of the different morphologies was analyzed. The results show that when the concentration of SiCw in the bath is 1.2 g/L, the surface of the Cu/SiCw composite coating prepared by the CuSO4 bath has more whiskers with irregular distribution and the coating is very smooth, but there are pores at the junction of the whiskers and Cu. There are a large number of irregularly distributed whiskers on the surface of the Cu/SiCw composite coating prepared with the copper methanesulfonate (Cu(CH3SO3)2) system. The surface of the composite is flat, and Cu grows along the whisker structure. The whisker and Cu form a good combination, and there is no pore in the cross-section of the coating. The observation at the cross-section also reveals some characteristics of the toughening mechanism of SiCw, including crack deflection, bridging and whisker pull-out. The existence of these mechanisms indicates that SiCw plays a toughening role in the composites. A suitable plating solution system was selected for the preparation of high-performance Cu/SiCw thermal management materials with the composite electrodeposition process.