The atomic structure of the Ca induced Si(111)-(3×2) surface at 300 K has been investigated using X-ray photoelectron diffraction (XPD). After confirming the quality of the single-domain (3×2) surface by LEED, in which weak ×2 streaks were observed likewise the patterns reported in the literature, we have measured the Ca 2p core-level spectra within an azimuthal angle range of ±66°, where 0° corresponds to the direction perpendicular to the Ca chain, and at takeoff angles from 9° to 15° using the Mg Kα line. The experimental XPD patterns showed good agreement with the simulated XPD patterns of the T₄ site model, while the simulated XPD patterns of the H₃ model do not agree with the experimental results. Taking these results into account, we conclude that Ca atoms are adsorbed on the T₄ site at 300 K and thus that the weak ×2 streaks do not result from the presence of two adsorption sites as proposed in the literature. [DOI: 10.1380/ejssnt.2006.166]