A new derivative of 3,4-propylenedioxyselenophene bearing naphthalenylmethyl appeandages on the bridge, called 3,4-dihydro-3,3-bis((naphthalen-2-yl)methyl)-2H-selenopheno[3,4-b][1,4]dioxepine (ProDOS-Np-2), was synthesized and polymerized via potentiostatic and potentiodynamic methods. The electrochemically obtained polymer film (PProDOS-Np-2) is pure blue at the neutral state and highly transparent at the oxidized state. An increase in the size of the substituents on the bridge resulted in an increase in the optical contrast ratio. Upon moving from naked bridge to benzyl and to naphthalenylmethyl substituents on the bridge center, the optical contrast changed from 51% to 65% and finally to 84%, which is the second highest reported optical contrast ratio in polyselenophene family. When compared to polythiophene analogue, the PProDOS-Np-2 has lower oxidation potential and band gap, higher optical contrast ratio, coloration efficiency, robustness, and stability. The polymer film preserved its properties even after thousands of cycles under ambient conditions.