A series of electrochromic N-substituted poly(3,4-propylenedioxypyrrole)s (PProDOPs) are reported, which exhibit the combined properties of a high (>3 eV) electronic band gap, colored oxidatively doped forms, and easily accessible, low redox potentials. Utilizing methyl (Me), propyl (Pr), octyl (Oct), propanesulfonated (PrS), and ethoxyethoxyethanol (Gly) pendants, the absorbance of the π−π* transition of the resulting polymers is blue-shifted when compared to the nonderivatized parent. For example, in the case of poly(N-ethoxyethoxyethanol ProDOP) (N-Gly PProDOP), this transition displays a maximum at 306 nm (onset at 365 nm), providing a colorless and highly transparent neutral polymer with a luminous transmittance greater than 99% for a film thickness of about 200 nm. N-Substituted PProDOPs display very well-defined cyclic voltammograms, with E 1/2 < −0.1 V vs Fc/Fc+ (+0.2 V vs SCE), negative of the oxidation of water, as desired for materials having stable doped forms and long-lived redox switching properties. In addition, the presence of a sulfonate group at the end of the propyl chain in N-PrS PProDOP offers the possibility of self-doping along with water solubility of the polymer. As a result, N-PrS PProDOP exhibits a fast and regular growth even in the absence of supporting electrolyte. This new family of polymers has not only shown interesting electrochromic properties in the visible. Upon doping, a very strong absorption is observed in the near-infrared (NIR) with changes in transmittance up to 97%, extending the use of these polymers as the active layer in vis−NIR switchable devices.