Two most abundant sources with the highest anticancer activity of natural polymethoxyflavonoids were oxidated by dimethyldioxirane ( DMDO ) to polymethoxy flavonoids 9 and 10 respectively. 9 or 10 were condensed with α-acetylglucosyl bromide, α-acetylgalactosyl bromide or α-acetylrhamnosyl bromide in dilute NaOH (aq)/CHCl3 system through phase transfer catalytic glycosation reaction, and followed by deacetylation, four new polymethoxyflavonoids glycosides 1~4 were synthesized. The structures of all the synthesized compounds were characterized by 1HNMR, 13CNMR and MS spectra. This synthetic method has the advantages of easy availability of starting materials，simple operation．