The effects of indium composition and the thickness of the combined InGaAs/GaAs thin cap layer on the energy spectra and relative electron–hole alignment of InAs quantum dots (QDs) grown by metal organic vapor phase epitaxy (MOVPE) are investigated by photoelectrical spectroscopy in a semiconductor/electrolyte system. In structures with InAs QDs and an InGaAs strain reducing layer, the shift of the hole׳s wave function to the QDs׳ top was revealed, which indicates In enrichment of the area near the top of QD׳. In structures with an ultrathin GaAs cap layer a change of the sign of the built-in dipole moment was observed. This is explained by coupling effects of quantum-confined electrons with surface states.