The first enantioselective total synthesis of the structurally unique nortriterpenoid (−)-walsucochin B has been accomplished through the cationic polyolefin cyclization initiated by chiral epoxide. The core framework and the stereocenters in the natural product were all constructed in this step. A site-selective, late-stage free-radical halogenation and Seyferth–Gilbert homologation was adopted to install the acetylene moiety to synthesize the phenylacetylene. The absolute configuration of walsucochin B was confirmed through enantioselective total synthesis.