Si/poly(3,4-ethylenedioxythiophene) (PEDOT) core/shell nanowire arrays have been prepared by chemical etching of Si nanowires followed by vapor-phase polymerization of PEDOT as hybrid photoanodes for photoelectrochemical water-splitting. The PEDOT layer is employed as a multi-functional coating to prevent photocorrosion of Si nanowires, collect photogenerated holes and catalyze the water oxidation reaction. The amino silane modified Si nanowire surface improves PEDOT layer adhesion, and the resulting photoanode exhibits better photoresponse and improved stability. By tuning the length of the nanowires, we identify that the competition between the carrier recombination and catalytic water oxidation reaction is the primary factor determining the photoelectrocatalytic activity of the hybrid photoanode.