Electrochemical treatment has a significant effect on the properties of carbon fibers (CFs). In this study, the effect of mild electric field action on the microstructure and properties of polyacrylonitrile (PAN)-based high-modulus CFs (HMCFs) and high-strength CFs (HSCFs) was investigated. Under the action of a mild electric field, CFs did not show obvious defects, but their microstructure, mechanical properties and electrical properties were affected. For HMCFs, the graphitization degree in both axial and radial directions of the fibers had a decreasing trend, the grain spacing increased, and the grain size and degree of orientation decreased, which led to a decrease in the tensile strength, tensile modulus and axial conductivity. However, for HSCFs, the pattern of change was exactly opposite to that of HMCFs. The results of this study can provide useful guidance for optimizing the production process and surface modification of CFs.