A photoemission study of the interface between spin-cast films of a conducting polymer blend consisting of poly͑3,4-ethylenedioxythiophene͒ ͑PEDOT͒, poly͑4-styrenesulfonate͒ ͑PSS͒ and glycerol as an additive, and vacuum-evaporated hole transport layers ͑HTL͒ of 4,4Ј-bis͑carbazol-9-yl͒biphenyl, N,NЈ-diphenyl-N,NЈ-bis͑1-naphthyl͒-1-1Јbiphenyl-4,4Ј-diamine and N,NЈ-diphenyl-N,NЈ-bis͑3-methylphenyl͒-1,1Јbiphenyl-4,4Ј-diamine reveals a hole injection barrier between 0.5 and 0.9 eV at the glycerol-modified PEDOT-PSS/HTL interface. The measured energy barriers imply a reasonable charge injection, which is very encouraging for further development of the novel anode structures based on a conducting polymer/small molecule interface to be utilized in electro-optic applications such as organic light-emitting devices.