The kinetics of a-glucose hydrogenation on the catalyst containing Ru nanoparticles in the matrix of hypercrosslinked polystyrene was studied. Two routes of the hydrogenation reaction were revealed; their rates differ by several digits. The first route includes the interaction of a-glucose with the spilled-over hydrogen supplied by the catalyst; the second one includes classical interaction of the sorbed substrate with incident hydrogen from the reaction medium. A mathematical description of D-glucose conversion and the change of the catalyst activity by the first method of D-glucose hydrogenation were obtained. The most probable scheme of the process flow was suggested. The main kinetic parameters were calculated. The role of hydrogen spillover phenomenon in the kinetics of the processes is discussed.