The specific heat of Mn3−xFexSi was measured over a wide temperature range. Aside from the lattice and electronic specific heat components, another component had a significant contribution to the specific heat at low temperatures in the case of x = 0.2; however, its contribution decreased when x = 1.0. It is observed that the net component was retained at temperatures significantly higher than TN for both x. The XAFS spectra of the Mn K-edge for x = 0 not only indicated a smooth structure near the edge, but also an unusually small amplitude in the extended high energy region; however, these features disappeared with Fe doping. The specific heat and XAFS data were discussed in terms of the charge degree of freedom or electronic inhomogeneity.