High-resolution near-edge x-ray absorption fine structure (NEXAFS) at Mn K edge is employed to probe the local environment of Mn dopant in ZnO. First-principles supercell calculations are systematically made to obtain theoretical NEXAFS. Mn is found to substitute for Zn up to 5 at.%Mn in polycrystalline samples sintered at 1623 K in air. Presence of Mn3O4 is apparent for samples with higher Mn content. The NEXAFS does not change in the range of Mn concentration from 0.01 to 5 at. %, indicating the absence of Mn precipitates. The results are confirmed by examining the polarization dependence of the NEXAFS for a 5 at. %-doped ZnO thin film.