Photoluminescence (PL) measurements are presented for thin epitaxial layers of InAs, 2.5 A˚<d<36 A˚, grown on InP(100) by molecular beam epitaxy. The combination of efficient carrier capture and PL redshift with increasing InAs thickness clearly indicate the formation of InAs quantum wells on the InP surface. Data are also presented for InAs/InP structures capped with strained layers of either GaAs or In0.5Al0.5As. Since radiative recombination within the InAs layers can be distinguished from PL arising from both bulk and surface defects, this system allows us to monitor the quality of both the InAs/InP and InAs/air interfaces via their influence on the InAs quantum well luminescence.