In this work, we present the evolution of optical constants as a function of [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) concentration for conjugated poly(3-hexylthiophene)/[6,6]-phenylC(61)-butyric acid methyl ester composites. The PCBM concentration of the utilized samples varies from 1 to 50 wt %. The dielectric functions for all these composites reveal electronic structural changes as a result of the addition of PCBM. We have deconvoluted the contribution of the substrate using a two-layer Fabry-Perot structural model. The extracted optical properties contain crucial absorption peaks of singlet exciton states and vibronic sidebands for poly(3-hexylthiophene) (P3HT) conjugated polymer as well as two PCBM-related states at higher energies. With the addition of PCBM, we have observed a limit of 20 wt % PCBM beyond which two discrete energy levels (3.64 and 4.67 eV) appear in the spectrum. For the highest concentration composite, the results suggest that the interchain interactions provide a small excitonic contribution in the absorption spectrum at energies where the conjugated polymer absorbs (1.85-2.7 eV) and a strong rise of PCBM states (3.64 and 4.67 eV) which are responsible for the subsequent exciton dissociation. In addition, the energy gap between the higher occupied molecular orbitals and the lower unoccupied molecular orbitals of the highest concentration composite (50 wt %) is 1.85 eV. The tuning of the optical properties of P3HT with the addition of PCBM shows that ellipsometry can be used to monitor layer concentration toward optimization of plastic solar cells. (C) 2007 American Institute of Physics.