The early stages of nanoporous layer formation, under anodic conditions in the absence of light, were investigated for n-type InP with a carrier concentration of similar to 3 x 10(18) cm(-3) in 5 mol dm(-3) KOH and a mechanism for the process is proposed. At potentials less than similar to 0.35 V, spectroscopic ellipsometry and transmission electron microscopy (TEM) showed a thin oxide film on the surface. Atomic force microscopy (AFM) of electrode surfaces showed no pitting below similar to 0.35 V but clearly showed etch pit formation in the range 0.4-0.53 V. The density of surface pits increased with time in both linear potential sweep and constant potential reaching a constant value at a time corresponding approximately to the current peak in linear sweep voltammograms and current-time curves at constant potential. TEM clearly showed individual nanoporous domains separated from the surface by a dense similar to 40 nm InP layer. It is concluded that each domain develops as a result of directionally preferential pore propagation from an individual surface pit which forms a channel through this near-surface layer. As they grow larger, domains meet, and the merging of multiple domains eventually leads to a continuous nanoporous sub-surface region. (c) 2006 The Electrochemical Society. [DOI: 10.1149/1.2401029] All rights reserved.