In this paper, FeCrCoW alloys with different W contents (0.4, 2.1 and 3.4 at%) are designed and studied in order to overcome the existing shortcomings of resistance materials. These resistance materials have high resistivity and a low temperature coefficient of resistivity. It is observed that the addition of W has a remarkable effect on the phase structure of the alloy. In particular, when the W content is 3.4 at%, the single BCC phase of the alloy can be transformed into the BCC and FCC phase. Meanwhile, when analyzed by transmission electron microscopy, there are stacking faults and martensite in FeCrCoW alloy with W content of 3.4 at%. These features are related to excessive W content. In addition, the strength of the alloy can be improved, and the ultimate tensile strength and yield strength are both very high, which are considered as grain-boundary strengthening and solid solution strengthening, caused by the addition of W. The electrical resistivity of the FeCrCoW alloys decreases when the content of W is more than 2.1 at%. The maximum resistivity of the alloy is 170 ± 1.5 μΩ·cm. Moreover, the unique properties of the transition metal allow the alloy to have a low temperature coefficient of resistivity in the temperature range of 298~393 K. The temperature coefficient of resistivity values of the W0.4, W2.1 and W3.4 alloys are −0.0073, −0.0052 and −0.0051 ppm/K. Therefore, this work provides a vision for resistance alloys, which can achieve highly stable resistivity and high strengths in a certain temperature range.