In this work, we utilized two fluorene-based polymers (F8TBTT and F8TTZT) as donor materials in organic photovoltaic cells (OPVs) and compared their performance to explain the effect of substituting fused thiazolothiazole for the bithiazole moiety. The OPV device based on F8TTZT showed a power conversion efficiency of 0.24%, which is three times higher than that of F8TBTT (0.07%) under the same conditions. The better performance can be explained by the increased planarity and enhanced intermolecular charge transport.