We investigate the efficiency and emission color of small-molecule based double-layer organic light-emitting diodes (OLEDs) based on 4,4'-bis[1-naphthyl (phenyl) amino]-1,1'-biphenyl (a-NPD) and aluminum (III) bis (2-methyl-8-quinolinato)4-phenylphenolato (BAlq) by studying the charge transport and photophysics near the organic–organic interface between the emitting layers. For that purpose, the light-emission profile is reconstructed from full angle, wavelength and polarization dependent electroluminescence spectra. By increasing the thickness of the BAlq layer from 100 to 300 nm, at a fixed 160 nm a-NPD layer thickness, the emission color is found to vary from deep blue to green, yellow-green, white and back to blue. We demonstrate that this is due to a gradual emission profile shift, in combination with a wavelength and layer thickness dependent light outcoupling efficiency. The emission profile shift, from an approximately 20 nm-wide zone on the a-NPD-side of the interface to a very narrow zone on the BAlq-side of the interface, gives rise to a changing balance between the contributions from BAlq excitons, a-NPD excitons and charge-transfer excitons. It also contributes to a pronounced layer thickness dependence of the external quantum efficiency. The shift of the emission profile is explained by a charge transport and recombination model.