This review summarizes the new carbon-carbon bond construction methods based on the radical reaction of imine derivatives. The intermolecular carbon radical addition to oxime ethers proceeded smoothly in the presence of BF3.OEt2. A high degree of stereocontrol in the reaction of oxime ethers was achieved to give amino acid derivatives with excellent diastereoselectivities. The radical reaction of imine derivatives in water has also been investigated. The radical cyclization of oxime ethers proceeded effectively to provide the functionalized heterocycles via a carbon-carbon bond-forming process. These reactions were extended to the solid-phase radical reactions using triethylborane or diethylzinc as a radical initiator.