We have developed a new germanium-bridged heptacyclic arene, dithienogermolocarbazole (DTGC), in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole core by two dibutylgermanium bridges. The germole moieties embedded in the DTGC structure were successfully constructed by one-pot nucleophilic cyclization in a high yield of 88%. Because of the relatively lower polarity of carbon-germanium bonds, the DTGC unit is chemically stable under basic conditions, rendering its more versatile functionalization. Comparison of germanium-bridged DTGC with the carbon-bridged DTCC (dithienocyclopentacarbazole) and silicon-bridged DTSC (dithienosilolocarbazole) analogues reveals that the HOMO energy level of DTGC lies between those of DTCC and DTSC and so does the LUMO energy level of DTGC. Density functional theory (DFT) calculations suggest that DTSC and DTGC have more bent structures than DTCC, which plays an important role in determining their frontier orbital energies. The structural disparity could be amplified in their corresponding polymers. The DTGC unit was copolymerized with four different comonomers, including benzothiadiazole (BT), dithienylbenzothiadiazole (DTBT), difluorobenzothiadiazole (FBT), and dithienyldifluorobenzothiadiazole (DTFBT) to yield a series of new alternating donor-acceptor copolymers, poly(dithienogermolo-carbazole-alt-benzothiadiazole) (PDTGCBT), poly(dithienogermolocarbazole-alt-dithienylbenzothiadiazole) (PDTGCDTBT), poly(dithienogermolocarbazole-alt-difluorobenzothiadiazole) (PDTGCFBT), and poly(dithienogermolocarbazole-alt-dithienyldifluorobenzothiadiazole) (PDTGCDTFBT). Because of the two additional thiophene rings in the repeating units on the backbone to facilitate -electron delocalization, PDTGCFDTBT showed a lower optical band gap than PDTGCFBT. Furthermore, PDTGCDTFBT also showed the lower-lying LUMO and HOMO energy levels than PDTGCDTBT as a result of the electron-withdrawing fluorine atoms. Consequently, the bulk heterojunction solar cell incorporating PDTGCDTFBT delivered the highest performance with Voc of 0.84 V, Jsc of 9.87 mA/cm2, FF of 48.8%, and PCE of 4.05%. By adding 3 vol % 1-chloronaphthalene to tailor the morphology, the solar cell using PDTGCDTFBT with higher molecular weight exhibited the improved efficiency of 4.50% with a Voc of 0.84 V, a Jsc of 11.19 mA/cm2, and an FF of 47.7%.