A series of oligo(thienylenevinylene) derivatives with or without thieno[3,2‐b]thiophene analogs as cores and three types substituent has been investigated at the PBE0/6‐31G(d) and the TD‐PBE0/6‐31+G(d,p) levels to design materials with high performance such as suitable frontier molecular orbital (FMO) energies to match those of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) and its derivatives, broad absorption spectra, higher and balance transfer property, and better stability. The results reveal that fused cores have slight effects on photophysical properties of investigated derivatives. The electron‐withdrawing or push–pull substituents result in red shifts of absorption spectra and better stabilities for investigated derivatives. The calculated reorganization energies of designed derivatives suggest them to be good potential ambipolar transport materials under the proper operating conditions. The promising donors for PCBM, bisPCBM, PC70BM, and indene‐C60 bisadduct (ICBA) as acceptors are recommended theoretically for solar cells based on the proper match for FMOs between donors and acceptors. Moreover, we have also predicted the mobility of designed molecule with better performance. © 2012 Wiley Periodicals, Inc.