Hot deformation experiments of as-cast 35CrMoV steel, with strain rates of 0.01 s−1 and 10 s−1, deformation temperatures of 850, 950, and 1050 °C, and an extreme deformation reaching 50%, were carried out using a Gleeble-3810 thermal simulator. Electrochemical corrosion experiments were conducted on the deformed specimens. The microstructure was observed by optical microscope (OM), and the corrosion morphology and corrosion products of the specimens were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS), confocal laser scanning microscopy (CLSM), and X-ray diffraction (XRD) techniques. The results show that the grain size increased gradually with an increase in the deformation temperature at the same strain rate, whereas the corrosion resistance deteriorated. At the same deformation temperature, the grain size becomes smaller as the strain rate increases, which enhances the corrosion resistance. This is mainly attributed to the fine grains, which can form more grain boundaries, increase the grain boundary area, and accelerate the formation of the inner rust layer at the beginning of corrosion. Moreover, fine grains can also refine the rust particles and enhance the bonding strength between the inner rust layer and the matrix. The denseness and stability of the inner rust layer increases as the corrosion process progresses, thereby improving corrosion resistance.