Catalytic amounts of heteropoly acids and polyoxometalates promoted mononitration of phenolic compounds using iron(III) nitrate nonahydrate and bismuth(III) nitrate pentahydrate in dichloromethane at room temperature. Tungstophosphoric acid cesium salt, Cs2.5H0.5PW12O40, in a heterogeneous phase, exhibited significant rate enhancement of reactions as well as ortho selectivity without over-nitration and oxidation byproducts.