The ultrafast charge carrier dynamics of alkyl-substituted thienylenevinylene and phtalimide-based donor/acceptor (D/A) alternating copolymer (PTVPhI-Eh) as well as PTVPhI-Eh:PC17BM bulk hetero-junctions (BHJs) with and without processing 1-chloronaphthalene (CN) additive have been studied by means of a femtosecond transient absorption (TA) measurement. Photo induced absorption of the D/A copolymer was prohibited under certain excitation intensity. In both BHJs, we observed fast decay components (similar to 1 ps) which are assisted by high order process such as exciton-charge annihilation (ECA) or exciton-exciton annihilation (EEA) under high excitation intensity. In the CN-treated BHJ, however, the fast decay components were shortened to <1 Ps because of increased ECA or EEA rate. In addition, the CN-treated BHJ showed slow geminate recombination time which indicates reduced carrier loss. Consequently, we could confirm excited stated properties of the copolymer and ultrafast spectroscopic evidences of enhancement in power conversion efficiency related with the inclusion of solvent additive to BHJ. (C) 2015 Elsevier Ltd. All rights reserved.