The present invention relates to a poly(2-vinylpyridine)-b-poly(n-hexylisocyanate) amphiphilic coil-rod block copolymer and a polymerization method thereof, more particularly to a poly(2-vinylpyridine)-b-poly(n-hexylisocyanate) amphiphilic coil-rod block copolymer polymerized by a process comprising synthesizing poly(2-vinylpyridine) having a narrow molecular weight distribution by living polymerization using potassium diphenylmethane (K-DPM) as initiator, adding sodium tetraphenylborate (NaBPh4) to replace the counter cation with a sodium ion (Na+) and adding n-hexylisocyanate and performing polymerization and a polymerization method thereof. According to the present invention, it is possible to control the molecular weight and the structure of each block of the copolymer. Therefore, coil-rod type amphiphilic block copolymers having a variety of structures can be obtained. The resultant block copolymer is a useful optical polymer material.