Herein, we report polybenzodioxane polymer (PIM-1), a multifunctional n-type emitter with strong green luminescence, and its suitability as an electron transport layer for OLEDs devices. The BrunauerEmmett-Teller (BET) test and photo-electrical properties of as-synthesized PIM-1 confirm the presence of large microporosity and excellent electron mobility. The photoluminescence (PL) spectroscopy shows the intense green emission at 515 nm upon 332 nm excitation wavelength. Moreover, the Hall effect study reveals the negative Hall resistivity, which indicates that PIM-1 possesses n-type semiconductor . Additionally, the electron mobility is found to be 4.4 Â 10 À6 cm 2 V À1 s À1 . Hence, these results demonstrate that PIM-1 could be an ultimate choice as an n-type emitter for the next generation of advanced electronic devices.