Tuning the electrochemiluminescence (ECL) wavelength of carbon dots (CDs) with enhanced efficiency is essential for multiplexed biosensing, bioimaging, and energy applications but remains challenging. Herein, we reported a facile route to finely modulate the ECL wavelength of CDs from 425 to 645 nm, the widest range ever reported, along with a more than 5-fold enhancement of ECL efficiency via phosphorous (P) incorporation. The molecular mechanism was explored experimentally and theoretically, which revealed the unusual dual roles of P dopants in the form of P-C and P-O bonding, that is, importing shallow trapping states and promoting an effective intramolecular charge transfer. This work would allow unlocking the key factors of ECL kinetics for heteroatom-doped CDs appearing out of reach and open a new avenue for the rational design of nanocarbon for desirable applications.