The atomic structures and chemical states of active and inactive dopant sites in n-type and p-type 4H-SiC(0001) substrates have been investigated by X-ray absorption near edge structure (XANES) and photoelectron spectroscopy (PES). In N atom-doped n-type 4H-SiC(0001), the PES results indicated that a N− C species was formed near the surface. XANES simulations showed that SiNx and N−C species were attributed to active and inactive dopant states, respectively. Angle-resolved XANES measurements showed that the N−C species acted as an inactive dopant site in N-doped 4H-SiC(0001). In Al-doped p-type 4H-SiC, PES analysis revealed that a single chemical state was present at the Al-doped 4H-SiC. The simulated XANES spectra showed that the Si site in 4H-SiC(0001) was replaced by an Al dopant atom, which was the active dopant site. Furthermore, relaxation of the local structure around the Al dopant in Al-doped 4H-SiC(0001) was observed due to bond stretching.