The wear of metal cutting tools is known to take place by the combined and simultaneous effects of several wear mechanisms. Knowledge of the relative contribution of the individual wear mechanisms is required to understand and predict the tool wear during cutting different workpiece materials and alloys. It has been shown previously that machining two heat resistant superalloys, alloy 718 and Waspaloy, leads to distinctively different tool wears. Even though the subject has been addressed in various studies, there are still open questions regarding the underlying reasons for the differing tool wear rates. In particular, the relative contributions of diffusion/dissolution when machining the two alloys have not been addressed so far. Therefore, a qualitative comparison of the chemical interaction between the tool material and the two superalloys was made by using diffusion couple tests. The aim was to mimic the high temperatures and intimate contact between workpiece and tool material at the tool rake and flank faces during cutting under controlled and static conditions. The obtained results suggest that it is unlikely that differences in flank wear rate when machining the two superalloys are caused by significantly varying magnitudes of tool atoms dissolving into the respective workpiece. Analysis of the tool/superalloy interfaces in the diffusion couples revealed diffusion-affected zones of similar size for both tested superalloys. Increasing test temperature led to enhanced interdiffusion which suggests an increase in tool wear by diffusion/dissolution for higher cutting temperature. For alloy 718, the higher test temperature also led to depletion of carbon together with formation of tungsten within the tool in close vicinity to the interface with the superalloy.