The physico-chemical properties of native oxide layers, spontaneously forming on crystalline Si wafers in air, can be strictly correlated to the dopant type and doping level. In particular, our investigations focused on oxide layers formed upon air exposure in a clean room after Si wafer production, with dopant concentration levels from ≈10 13 to ≈10 19 cm –3 . In order to determine these correlations, we studied the surface, the oxide bulk, and its interface with Si. The surface was investigated using the contact angle, thermal desorption, and atomic force microscopy measurements which provided information on surface energy, cleanliness, and morphology, respectively. Thickness was measured with ellipsometry and chemical composition with X-ray photoemission spectroscopy. Electrostatic charges within the oxide layer and at the Si interface were studied with Kelvin probe microscopy. Some properties such as thickness, showed an abrupt change, while others, including silanol concentration and Si intermediate-oxidation states, presented maxima at a critical doping concentration of ≈2.1 × 10 15 cm –3 . Additionally, two electrostatic contributions were found to originate from silanols present on the surface and the net charge distributed within the oxide layer. Lastly, surface roughness was also found to depend upon dopant concentration, showing a minimum at the same critical dopant concentration. These findings were reproduced for oxide layers regrown in a clean room after chemical etching of the native ones.