Laser drilling is always accompanied by recast layers, micro-cracks, and heat-affected zones, which limit its application in engineering. Due to its unique advantages, such as no heat-affected zones, no residual stresses, and no dependence on the mechanical properties of the materials, electrochemical dissolution has been adopted to remove the laser drilling-induced surface defects. The electrochemical dissolution characteristics and surface evolution of the laser-drilled Ni-based superalloys were studied. The polarization curves and electrochemical impedance spectroscopy (EIS) of the laser-drilled materials and the substrate were measured, indicating that the laser-drilled surface had a smaller corrosion resistance than the original substrate. X-ray photoelectron spectroscopy (XPS) results showed that the laser-drilled surface had a much higher oxygen content than the substrate. Additionally, electric current efficiency curves were obtained to study the anodic dissolution behavior of Ni-based superalloys. An electric current density in the 5–40 A/cm2 range was preferred to enhance the electrochemical dissolution rate. Moreover, the effects of electric current densities and post-processing time on the surface roughness and the recast layer thickness of the laser-processed Ni-based superalloys were investigated using a NaCl and NaNO3 solution electrolyte. The evolution of the surface quality and recast layer thickness were clarified. Furthermore, an anodic dissolution model of the laser-processed surface was established to illustrate the electrochemical post-processing mechanisms. Results revealed that electrochemical dissolution could completely remove the laser drilling-induced surface defects in 20 s using a 12.5 wt.% NaNO3 solution electrolyte and a 40 A/cm2 electric current density. Finally, an electrochemical post-processed surface with surface roughness (Ra) of 1.7 µm and without a recast layer was achieved. Micro holes without recast layers and Ra of 0.69 µm were obtained with high efficiency using laser processing and electrochemical post-processing.