A phosphorous-rich structure is generated on the InP (001) surface during metalorganic vapor-phase epitaxy. It consists of phosphorous dimers, alkyl groups, and hydrogen atoms adsorbed onto a layer of phosphorous atoms. The adsorbed dimers produce c(2×2) and p(2×2) domains, with total phosphorous coverages of 2.0 and 1.5 ML. The alkyl groups and hydrogen atoms adsorb onto half of the exposed phosphorous atoms in the first layer. These atoms dimerize producing a (2×1) structure. It is proposed that the first layer of phosphorous atoms is the active site for the deposition reaction, and that the organometallic precursors compete with phosphorous dimers, alkyl radicals, and hydrogen for these sites during growth.