A nonenzymatic one-step procedure for the chemo- and regioselective acylation of carbohydrates has been developed. With 1 mol % of an organocatalyst, acylation of octyl beta-D-glucopyranoside took place preferentially on the secondary hydroxy group at C(4) among four hydroxy groups including the primary hydroxy group at C(6) in 99% selectivity and in 98% yield. This could be alternatively achieved by a conventional protection/deprotection procedure via five steps and in 46% overall yield. Thus, development of the present process is expected to contribute to extremely shorten synthetic steps of carbohydrates.