For the purpose of synthesis of naturally occurring β- d-glucopyranoside, direct β-glycosidation for seven kinds of the functionalized primary alcohol in the presence of d-glucose using native or immobilized β-glucosidase (EC 3.2.1.21) from almonds under equilibrium condition was carried out. The utilization of high concentration of the alcohol acceptor, 3-methyl-2-buten-1-ol ( 3) or 2-methyl-2-propen-1-ol ( 4) using the immobilized enzyme gave the corresponding β- d-glucopyranoside ( 21, natural product) or ( 22) in 65 or 51% yield, respectively. On the other hand, the utilization of 4-equivalents of the functionalized alcohols ( 5– 9) using the immobilized enzyme in 90% tert-butanol/H 2O solution afforded the naturally occurring β- d-glucopyranosides ( 23– 27), respectively, in moderate yield. Among them, five kinds of β- d-glucopyranosides ( 21, 22, 24, 25, and 27) were converted into the cyanoglucosides (rhodiocyanoside A ( 28), osmaronin ( 29)) and other naturally occurring β- d-glucopyranosides ( 30– 32), respectively.