Wavelength-dependent two-photon photoemission (WD-TPPE) spectroscopy was used to investigate the surface state properties of CdTe crystals before and after the adsorption of specially designed organic molecules. One photon was used to modify the population of the surface states and a second photon to eject electrons from the substrate. We measured the dependence of the photoemission signal on the energy of the first photon and on the delay between the two light pulses. The energy of surface states, relative to the bands, was found to correlate with the relaxation time of the semiconductor surface after being photoexcited. This is explained in terms of a simple kinetic model for electron transfer. These findings demonstrate that the properties of surface states of semiconductors can be manipulated by adsorbing suitable organic molecules on the semiconductor surface and that the WD-TPPE method is a useful tool for optoelectronic characterization of semiconductor surfaces, with sensitivity exceeding that of most commonly used techniques.