The emerging field of tandem polymer solar cells (TPSCs) enables a feasible approach to deal with the fundamental losses associated with single-junction polymer solar cells (PSCs) and provides the opportunity to propel their overall performance. Additionally, the rational selection of appropriate subcell photoactive polymers with complementary absorption profiles and optimal thicknesses to achieve balanced photocurrent generation are very important issues which must be addressed in order to realize paramount device performance. Here, two side chain fluorinated wide-bandgap π-conjugated polymers P1 (2F) and P2 (4F) in TPSCs have been used. These π-conjugated polymers have high absorption coefficients and deep highest occupied molecular orbitals which lead to high open-circuit voltages (Voc) of 0.91 and 1.00 V, respectively. Using these π-conjugated polymers, TPSCs have been successfully fabricated by combining P1 or P2 as front cells with PTB7-Th as back cells. The optimized TPSCs deliver outstanding power conversion efficiencies of 11.42 and 10.05%, with high Voc's of 1.64 and 1.72 V, respectively. These results are analyzed by balance of charge mobilities, and optical and electrical modeling is combined to demonstrate simultaneous improvement in all photovoltaic parameters in TPSCs.