By grinding 1,4-dialkoxybenzene with anhydrous FeCl3 powder using a glass pestle in a mortar at ambient and solvent-free condition, poly(p-phenylene)s (PPP) was obtained in high yield up to 90% in 30 min. The products were characterized by H-1 NMR, C-13 NMR, WAXD, and UV-vis and the regioregular structure was suggested. The solid-state oxidative coupling polymerization is a facile, time saving, "green-chemistry" method.