A chemical investigation of the inner bark of Betula pubescens has led to the isolation of rhododendrin, epirhododendrin, apiosylrhododendrin and apiosylepirhododendrin. This is the first observation of both (+)- and (-)-rhododendrol glycosides in the same species. Also, the new compounds 3,4,5-trimethoxyphenyl-6-O-vanilloyl-beta-D-glucopyranoside and 3,4,5-trimethoxyphenyl-6-O-syringoyl-beta-D-glucopyranoside, and the known 4-O-beta-D-glucoside of p-hydroxybenzoic acid, as well as (+)-catechin, catechin 7-O-beta-D-xylopyranoside and B1 and B3 procyanidins were found.