The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm2O3-Bi2O3-B2O3 system were clarified. The crystalline phases of Bi4B2O9, Bi3B5O12, BiBO3, SmxBi1-xBO3, and SmB3O6 were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO3 and SmxBi1-xBO3 showed SH generations. The formation of the nonlinear optical BiB3O6 phase was not confirmed. The formation (writing) region of crystal fines consisting of SmxBi1-xBO3 by YAG laser irradiation was determined, in which Sm2O3 contents were similar to 10 mol%. The present study demonstrates that Sm2O3-M2O3-B2O3 glasses are promising materials for optical functional applications.