(1) Background: Boron-based diffusion layers possess great application potential in forging and die-casting due to their favorable mechanical and thermophysical properties. This research explores the enhanced wear resistance of tungsten hot-work steel through boriding and boroaluminizing. (2) Methods: Thermal-chemical treatment (TCT) of steel H21 was carried out. Pure boriding was introduced to the substrate through heating a paste of boron carbide and sodium fluoride 1050 °C for two hours. As for boroaluminizing, 16% of aluminum powder was added to the boriding paste. (3) Results: It was shown that boriding resulted in the formation of an FeB/Fe2B layer with a tooth-like structure. A completely different microstructure was revealed after boroaluminizing—namely, diffusion layer with heterogeneous structure, where hard components FeB and Mx (B,C) were displaced in the matrix of softer phases—Fe3Al and α-Fe. In addition, the layer thickness increased from 105 μm to 560 μm (compared to pure boriding). The maximum microhardness values reached 2900 HV0.1 after pure boriding, while for boroaluminizing it was about 2000 HV0.1. (4) Conclusions: It was revealed that the mass loss during wear test reduced by two times after boroaluminizing and 13 times after boriding compared to the hardened sample after five-min testing.