We present the structural and THz generation characteristics of the molecular salt crystal (E)-2-(4-(dimethylamino)styryl)-1,1,3-trimethyl-1H-benzo[e]indol-3-ium iodide (P-BI) using optical rectification with IR pump wavelengths. P-BI shows a peak-to-peak field ∼6 times greater than inorganic crystal GaP, and a broader THz spectrum. Data were obtained from 0-6 THz showing a significant dip in generation at 1.8 THz, similar to what has been observed with the THz generation crystal DAST at 1 THz. We characterized the power dependence of P-BI at different IR wavelengths, with optimal THz generation at the 1550-nm pump wavelength. To model THz generation as a function of P-BI crystal thickness, we measured the THz complex refractive index and the IR group index; modeling shows that imperfect phase matching leads to spectral narrowing centered at ∼2.5 THz as the crystal thickness is increased. P-BI could provide a useful alternative to inorganic THz generation crystals such a GaP.