A simple electrochemical approach based on potential sweeping has been developed for growing poly(phenylene sulfide) (PPS) brushes from 4,4'-disulfanediyldibenzenediazonium salt on glassy carbon and stainless steel. First, the diazonium salt becomes reduced at the substrate on the initial part of the sweep carried out in a negative direction to form a covalently bonded diphenyl disulfide film. Once sufficiently extreme potentials are reached the disulfide bridges are reductively cleaved to form a thin layer of covalently attached thiophenolates. These are prone to be involved in fast coupling reactions with the diazonium salt to form PPS brushes in a repetitive growth process. In this manner linear PPS brushes with thicknesses up to 150 nm are easily formed. In addition, exact con-trol on the brush length may be exerted through the switching potential selected or the number of sweeps applied. The films are characterized by time-of-flight secondary ion mass spectrometry which shows that the film growth is accompanied by an increase in the intensity ratio of S-/S-2 in line with the proposed PPS structure. This structure was further supported by Raman spectra, exhibiting a high-intensity C-S stretch band and no S-S stretch band. (C) 2015 Wiley Periodicals, Inc.