We investigate the influence of annealing conditions on the physical properties of thin films of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT/PSS). In particular, we describe how annealing temperature, the ambient gas, and choice of dopant affect the conductivity, morphology, and work functions of the films. Two specific dopants are considered, sorbitol and glycerol, and broad guidelines are developed for using PEDOT/PSS as a hole-injection electrode in polymeric light-emitting devices, solar cells, and photodetectors.