Coupling of benzyl bromide giving 1,2-diphenylethane was demonstrated to proceed at room temperature in THF solution mediated by the potassium/18-crown-6 supramolecular complex. Based on this model reaction a novel method for the low temperature synthesis of poly(p-xylylene) from alpha,alpha'-dibromo-p-xylene is proposed. Experimental evidence of the polymer structure was provided by solid-state C-13 NMR and IR spectroscopy.