In this study, six different donor‐π‐acceptor1‐π‐donor‐acceptor2 type random co‐polymers containing benzodithiophene as a donor, benzooxadiazole (BO), and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) as acceptor, have been synthesized and characterized. In addition to the acceptor core ratio at different values, the effect of aromatic bridge structures on the optical, electronic, and photovoltaic properties of six different random co‐polymers is investigated by using thiophene and selenophene structures as aromatic bridge units. To investigate how the acceptor unit ratio and replacement of aromatic bridge units impact the structural, electronic, and optical properties of the polymers, density functional theory (DFT) calculations are carried out for the tetramer models. The open‐circuit voltage (VOC), which is strongly correlated with the HOMO levels of the donor material, is enhanced with the increasing ratio of the TPD moiety. On the other hand, the short‐circuit current (JSC), which is associated with the absorption ability of the donor material, is improved by the increasing ratio of BO moiety with the π‐bridges. BO moiety dominant selenophene π‐bridged co‐polymer (P4) showed the best performance with a power conversion efficiency (PCE) of 6.26%, a JSC of 11.44 mA cm2, a VOC of 0.80 V, and a fill factor (FF) of 68.81%.