The optical properties of narrow InGaAs/InP quantum wells and their dependence on the gas switching procedure during the metalorganic chemical vapor deposition growth process are studied. A transition from In1-xGaxAs monolayer to InAs1-xPx monolayer splitting is observed in the photoluminescence spectrum, if the AsH3 purging time of the InP surface is equal larger than 2 s. This transition is attributed to a P-As exchange at the lower interface (InGaAs on InP) leading to InAs1-xPx interfacial islands, which are larger than the excitonic diameter.