The first catalytic asymmetric cyclopropanation of diazo oxime ethers with olefins was developed. In the presence of a Ru(II)-Pheox catalyst, various optically active cyclopropyl oxime derivatives were obtained in high yields (up to 99%) with high enantioselectivities (up to 98% ee). Furthermore, optically active cyclopropyl oxime ethers could be successfully converted into the corresponding cyclopropyl methylamine derivatives via metal hydride and Grignard reagent mediated Beckmann rearrangement, which are potential candidates for the assessment of biological and pharmaceutical activities.