Case-hardening 14Cr14Co13Mo4 martensitic stainless steel needs to be carburized to improve surface performance. Low-pressure carburization has the benefit of having oxidation-free production and being ecofriendly. However, compared with the low-pressure carburization of the low-alloy steel, low-pressure carburization of the 14Cr14Co13Mo4 steel consumes more time and has a risk of network carbides. In order to promote carbon diffusion and avoid network carbide, Fe–Ni films with various thickness were electrodeposited on the 14Cr14Co13Mo4 steel prior to low-pressure carburization. The experimental results show that, under the same carburizing conditions, the surface carbon content decreases and the carburized layer increases with the increase of Fe–Ni film thickness. After the hardening heat treatment, the effective case depth (ECD) of the sample coated with 6.0 μm Fe–Ni film was increased by 29% compared to that of the uncoated sample. The morphology of carbides was a strip-shaped, discontinuous network distribution in the uncoated sample, while in the Fe–Ni coated samples, the carbides changed to a globular, uniformly dispersed distribution. The effect of Fe–Ni film on the low-pressure carburizing of steel is explained by the simulation of the carbon diffusion using DICTRA software. The Fe–Ni films reduce the steel surface carbon content in each boost stage of low-pressure carburizing and release carbon atoms in every diffusion stage. Through this adjustment mechanism, the steel surface carbon content can be reduced and carburized layer growth can be promoted.