Poly(β-alkoxy,naphthalene vinylene) (PAONV) was synthesized from β-naphthol and H(CH2)mBr(m=4,6,8,9) under ultrasonic irradiation.The influences of reaction conditions on the yield of intermediates and polymers were studied.The structure of intermediates and polymers were characterized with IR and 1H NMR spectroscopy.These results showed that the total yield of PAONV under ultrasonic irradiation was 70.0%—74.4%,higher than that under reflux stirring.The reaction time was shortened from 35 h to 20 h.The yield of etherification in the C2H5ONa system was higher than that in the NaOH system.The dimetyl sufoxide as a strong polar solvent favored the yield of dehydrochlorination.The best reaction times of etherification, chloromethylation, dehydrochlorination were 5 h,5 h,10 h,respectively.