Sorbitol hydrogenolysis was carried out over a carbon nanofiber supported ruthenium catalyst prepared by incipient wetness impregnation. The carbon nanofiber supported ruthenium catalyst was shown to have an attracting behavior when compared with a commercial activated carbon supported ruthenium catalyst, especially in terms of selectivity to glycols. The preferable hydrogen partial pressure for sorbitol hydrogenolysis was ca. 8.0 MPa, lower than that usually reported in previous works. Slightly soluble calcium hydroxide, which was used as a basic promoter, remarkably increased the selectivity to glycols, as compared with the soluble sodium hydroxide. The variation of product selectivity with catalyst amount indicated that glycerol was the initial C3 polyol product while propylene glycol was derived from glycerol. The parametric investigation was further focused on the intrinsic features of sorbitol hydrogenolysis. (C) 2009 Elsevier Ltd. All rights reserved.