Chemically treated Si(111) surfaces in aqueous NaF solution have been investigated using spectroscopic ellipsometry (SE), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and wettability measurements. The SE data indicate that the solution causes the removal of the native oxide upon immersing the sample in the solution. After the native oxide is etched away completely, the SE data yield the spectrum of a slightly roughened surface. The SE-estimated roughness is ∼ 0.64 nm, which is considerably larger than the AFM determined rms value (∼ 0.26 nm); the difference is considered to be due to the SE technique being sensitive not only to the surface microroughness but also to the adsorbed chemical species. The XPS data support the fact that the native oxide is removed upon immersing the sample in the solution. It is also shown that the Si LMM signal at ∼ 1160 eV can provide direct information regarding the relative quality of surface regions prepared by different methods. The wettability measurements show that the as-degreased surface is hydrophilic (θ ∼ 35 • ), while the NaF-etched surface is hydrophobic (θ ∼ 70 • ).