Chemically cleaned GaP͑001͒ surfaces in aqueous HF solutions have been studied using spectroscopic ellipsometry ͑SE͒, ex situ atomic force microscopy ͑AFM͒, x-ray photoelectron spectroscopy ͑XPS͒, wettability, and photoluminescence ͑PL͒ measurements. The SE data clearly indicate that the solutions cause removal of the native oxide film immediately upon immersing the sample ͑Յ1 min͒. The SE data, however, suggest that the native oxide film cannot be completely etch-removed. This is due to the fact that as soon as the etched sample is exposed to air, the oxide starts to regrow. The SE estimated roughness is ϳ1 nm, while the AFM roughness value is ϳ0.3 nm. The XPS spectra confirm the removal of the native oxide and also the presence of regrown oxide on the HF-etched GaP surface. The wettability measurements indicate that the HF-cleaned surface is hydrophobic, which is in direct contrast to those obtained from alkaline-cleaned surfaces ͑hydrophilic͒. A slight increase in the PL intensity is also observed after etching in aqueous HF solutions.