Solvent‐free cyanoethylation of selected alcohols with acrylonitrile (AN) using a weakly basic polymer resin, Amberlyst A‐21 (AA‐21) was studied at 75°C. The conversion of primary alcohols, 1‐octadecanol, hexane‐1,6‐diol, pentaerythritol, but‐2‐yne‐1,4‐diol, N‐methyldiethanolamine, triethanolamine and diethanolamine is higher than secondary alcohols, isopropanol and glycerol in the presence of polymer resin. Of various alcohols, but‐2‐yne‐1,4‐diol gave the product in high conversion (87%) in cyanoethylation with a polymer resin/AN weight ratio of 0.04. The polymer resin showed recycling ability only in two cycles to produce cyanoethylated product from diethanolamine. In case of 1‐octadecanol, hexane‐1,6‐diol, and N‐methyldiethanolamine with AN under similar conditions, no recycling ability was observed. Thermally treated polymer resin at 75°C afforded the product in lower conversion (55%) whereas the same product was obtained in 69% when fresh polymer resin was used in cyanoethylation of 1‐octadecanol. No catalytic effect was observed for polymer resin treated at 100°C. Fourier transform infrared (FTIR) spectra showed CN stretching at 2248 cm⁻¹ for the polymer resin collected after the reaction which was caused by the AN binding on polymer resin during the reaction. As per thermogravimetric curves, 5% weight loss was observed at 201°C for recovered resin and at 161°C for polymer resin treated at 100°C. Scanning electron microscope images confirmed the AN binding on polymer beads after catalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013