Abstract A general method for the regioselective Heck reaction of electron-rich olefins is presented. Fast, highly regioselective Pd-catalysed α-arylation of electron-rich olefins, vinyl ethers (1 a–d), hydroxyl vinyl ethers (1 e, f), enamides (1 g, h) and a substituted vinyl ether (1 i) has been accomplished with a diverse range of aryl bromides (2 a–r), for the first time, in cheap, green and easily available alcohols with no need for any halide scavengers or salt ...