A new strategy was devised to stereo-speclfically introduce various building blocks, mainly heterocydes such as pyri-midines and trlnzlnes onto a multi-hydroxy molecule. A glu-copyranoside was chosen as a target scaffold. Two polymer-based protective reagents were jointly integrated in the imple-mentation of the strategy. It was found that in the a-D-glu-copyranoside, which has four free hydroxyl groups within the same molecule, its 4, 6-di-OH could be simultaneously pro-tected by polystyryl boronie acid, which left the 2, 3-di-OH free for substitution. Due to the steric effects within the molecule, the 2-OH is much more liabile to electrophilic stub-stitutlon. Thus the first and the second building blocks could be introduced regioselectlvely onto the 2-OH and the 3-OH positions. After a facile deprotectlon, the 4,6-di-OH were left free and by application of a second protecting reagent-polystyryltrityichlorlde onto 6-OH, a third building block was introduced onto the 4-OH position. After further deprotec-tion, the fourth building block was later introduced onto the 6-OH position. The new strategy was successfully applied in the combinatorial synthetds by application of the split-mix technique. The respective eleven small Ebraries were obtained and confirmed by I-IPI_~MS and NMR. Some preliminary results on chemical structure/herbicidal activity relationship were discussed.