In this paper, a convenient procedure was discovered and optimized to synthesize 7-methoxy-4'-substituted flavones from 2-hydroxy-4-methoxyacetophenone and 4-substitutedbenzoyl chlorides. The four flavones were obtained via these reactions of esterification, rearrangement and cyclization. The esterification was carried out for 0.5 ~ 4 h at room temperature, with the mole ratio of 1:1~1:1.3 [n (2-hydroxy-4-methoxyacetophenone): n (4-substitutedbenzoyl chlorides)]; the rearrangement was performed for 2 ~ 6 h at 30 ~ 60℃; the cyclization was attained for 2 ~ 5 h at 80 ~ 100℃, with the catalyst of acetic acid / sulfuric acid (V/V = 15:1 ~ 20:1). Under the optimum reaction conditions, the target products were obtained in overall yields of 50% ~ 75% and purity of more than 95%. The structures of the compounds were confirmed by 1H NMR, IR and MS.