A synergistic approach combining new material design and interfacial engineering of devices is adopted to produce high efficiency inverted solar cells. Two new polymers, based on an indacenodithieno[3,2-b]thiophene-difluorobenzothiadiazole (PIDTT-DFBT) donor–acceptor (D–A) polymer, are produced by incorporating either an alkyl thiophene (PIDTT-DFBT-T) or alkyl thieno[3,2-b]thiophene (PIDTT-DFBT-TT) π-bridge as spacer. Although the PIDTT-DFBT-TT polymer exhibits decreased absorption at longer wavelengths and increased absorption at higher energy wavelengths, it shows higher power conversion efficiencies in devices. In contrast, the thiophene bridged PIDTT-DFBT-T shows a similar change in its absorption spectrum, but its low molecular weight leads to reduced hole mobilities and performance in photovoltaic cells. Inverted solar cells based on PIDTT-DFBT-TT are explored by modifying the electron-transporting ZnO layer with a fullerene self-assembled monolayer and the MoO3 hole-transporting layer with graphene oxide. This leads to power conversion efficiencies as high as 7.3% in inverted cells. PIDTT-DFBT-TT's characteristic strong short wavelength absorption and high efficiency suggests it is a good candidate as a wide band gap material for tandem solar cells.