Depth selective XAFS spectrometry was applied to determine the chemical states of phosphorus in atmospheric aerosols. Atmospheric aerosols were collected on aluminum foils and polyethylene films using a 4-stage cascade impactor and a 12-stage low pressure Andersen sampler, respectively. Samplings were performed at Uji (urban area) and Sakurajima (near a volcano). We measured X-ray fluorescence yield (XFY) and total electron yield (sample current) simultaneously to obtain the X-ray absorption near edge structure (XANES) spectra of the atmospheric aerosols. X-ray absorption in the vicinities of P K-edges was measured on the beamline BL-11B at the Photon Factory, High Energy Accelerator Research Organization, Tsukuba, Japan. The Sakurajima aerosol samples showed only a P⁵⁺ peak and the peak was remarkable in coarse mode. In case of the Uji samples, the P⁵⁺ peak was dominant and a slight P³⁺ peak was detected for sample current measurement.