The addition of a small amount of high boiling point solvent in organic donor/acceptor blends to control their morphology is a viable approach to enhance the power conversion efficiency of bulk heterojunction (BHJ) organic solar cells. Herein, through transient absorption spectroscopy (TAS) correlated with physical characterizations and device studies, we investigate the effects of a family of thiol-based additives (i.e., 1,5-pentanedithiol (PDT), 1,6-hexanedithiol (HDT) and 1,8-octanedithiol (ODT)) in P3HT:PCBM blend films in a bid to establish a morphology-function-charge dynamics relationship with their photovoltaic performances. The performance of solar cell devices (ηHDT = 2.8%, ηODT = 2.8%, ηPDT = 1.7%) is related to the additive-induced phase separation and the degree of ordering of P3HT. TAS uncovers a more efficient initial exciton and polaron generation in the additive-treated blend samples compared to the non-additive treated control sample. HDT and ODT-added blends exhibit decay dynamics and performances similar to those of the thermally annealed samples. However, the PDT-added blend exhibits a strong trap-assisted recombination in the subsequent nanosecond-microsecond timescales. We attribute this to the loss of charge carriers in the larger isolated P3HT domains due to the lack of percolation paths to the electrode. Our findings illustrate that understanding the complex interplay of the crystalline order, intermixed phases and percolation pathways is key to optimizing the performance of thermal-annealing free, additive-treated organic solar cells.