This paper studies the effect of mesostructured materials in the stereo-selective hydrogenation of 3-hexyne at 298 K and 40 psig pressure of H(2) over Pd-supported catalysts at different substrate:palladium (S:Pd) molar ratios. The catalysts were prepared by impregnation using a toluene solution of Pd(acac)(2) to obtain a metal content close to 1 wt.% over SBA-15 with one-dimensional hexagonal structure, MCM-48 silica with cubic structure and three-dimensional pore system and MSU-gamma alumina with a lathlike particle morphology. All the supports were characterised by nitrogen adsorption-desorption isotherms at 77K, TEM, XRD and H(2) chemisorption and TEM measurements. The reactions were found to be zero order with respect to 3-hexyne concentration. The starting 3-hexyne produces primarily cis-3-hexene, which subsequently is either hydrogenated to hexane or isomerized to trans-3-hexene and 2-hexenes that are found in very small amounts depending on the nature of the support used. Palladium catalysts supported on SBA-15 was the most active and selective catalyst. (C) 2010 Elsevier B.V. All rights reserved.