Herein we report chemoselective hydrogenation of furfural to furfuryl-alcohol over ABO3 inorganic perovskites containing inexpensive and abundant transition metals (LaMO3 M = Co, Mn, Fe). Firstly, the perovskite catalysts were fully characterized and found to have surface areas ranging from 10 to 30 m2/g. Secondly, the anionic defects within the perovskite lattices were determined using X-ray photoelectron spectroscopy (XPS) and Density Functional Theory (DFT) calculations and quantified in terms of the amount of oxygen vacancies. The catalysts with the highest amount of oxygen vacancies were found to be the least active in the hydrogenation of furfural at high H2 pressure.