Two-dimensional electron gas is precisely confined at the interface of insulating oxide thin films and substrates, e.g., LaAlO3/SrTiO3(STO) and, thus, shows 2D electronic transport features. Here, we report a high mobility electron state at the interface of a Cr2O3 film and a STO substrate, which is realized by depositing a Cr film onto a STO (111) substrate in high vacuum (1 × 10−10 mbar) using molecular beam epitaxy. At a substrate temperature of 700 °C, the deposited Cr films capture oxygen atoms from STO substrates, resulting in the formation of an insulating Cr2O3 layer and an oxygen-deficient STO layer. Due to the presence of high mobility electrons [1.5 × 104 cm2V−1 s−1 at 1.8 K] at the Cr2O3/STO interface, both out-of-plane and in-plane Shubnikov–de Haas oscillations are observed at low temperatures (<3 K), which suggests that the highly conducting electron gas has extended into the STO bulk along the thickness direction with a certain depth to allow electrons to complete the cyclotron motion.