Polymerization behavior of delta-valerolactone (VL) with alkylsamarium (RSmI(2)) was studied, and its application to the block copolymerization of tetrahydrofuran (THF) with VL was examined. Polymerization of VL by butylsamarium gave the corresponding poly(VL) in good yield. The yield increased with increasing the concentration of VL and decreasing the polymerization temperature, resulting from the equilibrium between VL and poly(VL). The decrease in the molecular weight of poly(VL) by prolonging the polymerization time indicated the existence of back-biting reaction to form cyclic oligomers. The polymerization of VL with poly(THF)-macroanion obtained by the two-electron reduction of the propagation center of living poly(THF) with SmI2 led to the block copolymer of THF with VL. The initiation efficiency of VL-polymerization was almost quantitative, and the unit ratio of THF and VL-segments could be controlled by both the polymerization time of THF and the amounts of VL.