The work aims to prepare TaSe2/MoS2 heterogenous composite coating with ultralow friction coefficient in air environment and study the impact of different relative humidity on the tribological properties of the coating. TaSe2/MoS2 heterogenous composite coating and MoS2 coating were prepared through spraying method based on the theory of heterogeneous superlubricity and the design concept of valence bond structure stability. Further, tribological properties of TaSe2/MoS2 heterogenous composite coating and MoS2 coating in air with different relative humidity were studied. The surface morphology of wear tracks and transfer films of TaSe2/MoS2 heterogenous composite coating and MoS2 coating were studied and compared by the optical microscopy. Then, the wear rate of these two coatings was studied by 3D profilometer. To reveal the tribological mechanism of heterogenous coating, the distribution of chemical elements on the wear tracks and the degree of oxidation of TaSe2/MoS2 heterogenous composite coating and MoS2 coating under different relative humidity were analyzed by energy dispersive spectroscopy (EDS) and Raman spectroscopy. In addition, the chemical structure and composition of the wear tracks and transfer films of different coatings were also studied by EDS and Raman spectroscopy. The ultralow friction coefficient of TaSe2/MoS2 heterogenous composite coating was achieved in air with 10% RH, in which the friction coefficient was as low as 0.013. Although the friction of TaSe2/MoS2 heterogenous composite coating increased with the increasing relative humidity from 30% to 75%, it was still lower than that of MoS2 coating under the same testing conditions. The wear track depth and the wear rate of TaSe2/MoS2 heterogenous composite coating were all lower than those of MoS2 coating in air with different relative humidity, indicating that the overall tribological and anti-wear properties of TaSe2/MoS2 heterogenous composite coating were obvious better than those of MoS2 coating. Further, EDS and Raman patterns showed that the lubricant film of heterogeneous composite coating was composed of the coexistence structure of TaSe2 and MoS2, indicating the formation of heterogenous friction interface, which was important for achieving low friction coefficient. O contents of TaSe2/MoS2 heterogenous composite coating wear tracks in air with different relative humidity were also lower than that of MoS2 coating, which indicated that the oxidation degree of TaSe2/MoS2 composite coating was slight compared to MoS2. The intensity of MoO3 Raman characteristic peaks of different lubricating coating friction interfaces in 10% RH, 40% RH, and 75% RH could also prove the excellent oxidation resistance of TaSe2/MoS2 composite coating. It can be concluded that MoS2/TaSe2 heterogenous friction interface could prevent the MoS2 from oxidative damage, which is beneficial in the stable chemical structure of TaSe2. In summary, TaSe2/MoS2 heterogenous composite coating can exhibit ultralow tribological properties in 10% RH due to the existence of TaSe2/MoS2 heterogenous composite lubricating film. The chemical bond strength of Se-Ta is higher than that of S-Mo and difficult to be damaged by active molecules, so TaSe2/MoS2 composite lubricating film has better wear and oxidation resistance than MoS2 coating. A new heterogenous composite lubricity with ultralow friction is prepared in low relative humidity, which is important for the engineering application of superlubricity theory in air.