We present the synthesis and characterization of poly(2-alkyl-benzimidazole-alt-9,9-dihexylfluorene). An improved microwave-assisted synthesis of the monomers 4,7dibromo-2-heptyl-1H-benzo[d]imidazole and 4,7-dibromo-2-(heptan-3-yl)-1H-benzo[d]imidazole was developed. The monomers were polymerized with 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester using Suzuki cross-coupling to yield the corresponding poly(2-alkyl-benzimidazole-alt-9,9-dihexylfluorene)s. The polymers were characterized by both traditional optical and thermal properties in conjunction with experiments yielding strong evidence to suggest controllable chemical doping of benzimidazole moieties. Based on ultraviolet-visible spectroscopy (UV-vis) and cyclic voltammetry (CV) data, the band structure of these benzimidazole-containing polymers may be manipulated through treatment with acids or bases to achieve polycationic or polyanionic products. Protonic doping is shown to significantly impact the electronic properties of the parent polymer; the optical band gaps were shown to shift +0.07 and -0.33 eV for the acid- and base-doped polymers, respectively. Herein, we quantify the changes in band structure between the neutral and charged polymers.