A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study, and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol-1) and noncoplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C61 butyric acid methyl ester leads to a red shift in the absorption only for 1a and 2a. An interesting NIR electrochromism was found for 2 a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore, indicating a significant structural difference between the ground state and the excited state. Photoluminescence of the film of 2a was further probed at variable temperatures and the results strongly suggest that the restriction of bond rotations certainly helps to diminish non-radiative decay and thus enhance the luminescence of these large chromophores.