Liquid-phase oxidation of betulin extracted from birch bark was studied over gold catalysts supported on a range of supports (hydrotalcite, ZrO2, ZnO, MgO, CeO2, La2O3, HMS and various alumina) with different morphology and properties. Gold catalysts as well as the corresponding supports were characterized by XRD, BET, ICP-OES, XPS and TEM. It was found that the nature of the support plays a decisive role in betulin oxidation over gold-based catalysts, expressed in the influence on the average size and distribution of gold nanoparticles and, thereby, on their catalytic performance (activity and selectivity) in betulin oxidation. Moreover, it was revealed that betulin oxidation catalyzed by gold is a structure sensitive reaction, requiring an optimal size of gold nanoparticles of ca. 3.3 nm. The most suitable support for gold was found to be alumina. Kinetic studies allowed determination of reaction orders and conditions favorable for selective formation of a particular oxo-derivative of betulin (betulone, betulinic and betulonic aldehydes, betulinic acid).