The intermetallic compound Fe1−xCoxSi has a helical magnetic order for 0.05<x<0.8, whereas its orbital angular momentum contributing to the occurrence of a Dzyaloshinskii–Moriya interaction has not yet been verified. We applied soft x-ray magnetic circular dichroism spectroscopy on the Fe L2,3 and Co L2,3 edges below Tc for Fe0.75Co0.25Si such that their orbital magnetic moments morb were evaluated independently. The dichroic signals provide direct experimental evidence that morb for both Fe and Co is coupled in a parallel manner with each spin counterpart mspin. The ratio of morb to mspin is independently estimated as morb/mspin∼3% for Fe and 9% for Co. By comparing the average of the two mspin values with the saturated magnetization using a commercial superconducting quantum interference device (SQUID) magnetometer, the hole number in the d bands for both Fe and Co is roughly estimated as approximately 1.5. This suggests that Fe and Co should be arranged closely for stabilizing the ferromagnetic moments.