Either hardness or toughness has been the core interest in scientific exploration and technological pursuit for a long time. However, it is still a big challenge to enhance the hardness and toughness at the same time, since the improvement of one side is always at the expense of the other one. Here, we have succeeded in dealing with this pair of conflict based on tungsten (W) coating by doping boron (B) via magnetron co-sputtering. The results reveal that the introduction of low concentrations of B (6.3 at. %), in the doping regime, leads to the formation of W(B) supersaturated solid solution with refined grains. Meanwhile, the doping-induced higher compressive stress, higher H/E* and denser microstructure result in a surprising combination of improved hardness (2 × larger than pure W) and superior toughness (higher crack formation threshold compared to pure W). We believe this is an innovative sight to design new generation of transition-metal-based multifunctional coatings. Besides, our results are applicable for industrial application because it can be realized by simple manufacturing approaches, e.g. magnetron sputtering technology.