Aluminum-modified plasma nitriding was developed in this research by the addition of a few FeAl particles around samples of 42CrMo middle carbon alloy steel during plasma nitriding. The goal of this study was to enhance nitriding efficiency and the combined performance of the steel. The research results show that nitriding efficiency was greatly enhanced, by about 6 times, with the effective hardening layer rising from 224 μm to 1246 μm compared with traditional plasma nitriding at 520 °C/4 h. More importantly, the compound layer increased just a little bit, from 11.64 μm to 14.32 μm, which remarkably reduced the ratio of the compound layer’s thickness to the effective hardening layer’s thickness, thus being quite beneficial to decreasing the brittleness level, making the brittleness level decrease from Level 4 to Level 1. Also, extremely high surface hardness and excellent wear resistance were obtained by aluminum-modified plasma nitriding due to the formation of hard phases of AlN and FeAl in the nitrided layer, with the surface hardness rising from 755 HV 0.025 to 1251 HV 0.025 and the wear rate reducing from 8.15 × 10 −5 g·N −1·m −1 to 4.07 × 10 −5 g·N −1·m −1. In other words, compared with traditional plasma nitriding, wear resistance was enhanced by two times after aluminum-modified plasma nitriding. Therefore, this study can provide comprehensive insights into the surface characteristics and combined performance of aluminum-modified plasma nitriding layers.