Novel Pd catalysts based on fiberglass materials have been prepared, characterized by means of X-ray photoelectron spectroscopy and scanning transmission electron microscopy, and tested in the selective hydrogenation of acetylene in an excess of ethylene. The selectivity on fiberglass catalysts was found to change slightly with conversion in a wide range of temperatures and contact times, so that the ethylene increment was more than 56% at a complete conversion of acetylene. It was shown that high performance of the catalysts is caused by the ability of fiberglass materials to (i) stabilize very small Pd clusters (around 1 nm in size) in the glass matrix and (ii) absorb predominately polar and polarizable molecules, such as acetylene. (C) 2014 Elsevier B.V. All rights reserved.