A novel persulfate-mediated oxidative glycosylation system using p-methoxyphenyl (PMP) glycosides as bench-stable glycosyl donors is developed. This study shows that both K2S2O8 as an oxidant and Hf(OTf)4 as a Lewis acid catalyst play important roles in the oxidative activation of the PMP group into a potential leaving group. This convenient glycosylation protocol proceeds under mild conditions and delivers a wide range of biologically and synthetically valuable glycoconjugates, including glycosyl fluorides.