Graphitic carbon nitride (g-CN) is an attractive electrochemiluminescence (ECL) luminophore. However, g-CN with wavelength-tunable ECL emission is still limited, which limits its application in multicolor ECL sensing and imaging analysis. In this study, porous g-CN (PCN) with nitrogen defects was synthesized through the condensation of melamine by using o-fluorobenzoic acid (o-FBA) as an effective regulation reagent. A series of PCNs, including PCN-5%, PCN-10%, and PCN-30%, were obtained by changing the mass ratio of o-FBA and melamine. The porous structure and tunable chemical composition change of the PCNs were carefully characterized. The nitrogen defects and porous structure of the synthesized PCNs can enlarge the specific surface area, facilitate electron transfer, and generate various surface states with gradually changed energy bands, leading to wavelength-tunable multicolor ECL emissions. Accordingly, g-CN, PCN-5%, PCN-10%, and PCN-30% can generate navy blue, turquoise blue, turquoise green, and olive green ECL emissions, respectively, with the peak ECL wavelength varied from 465 to 550 nm. Then, a multicolor ECL sensing array was proposed for the discrimination of polyphenols based on the prepared g-CN and PCNs by using a smartphone as a portable detector for the first time. Five polyphenol substances including vitamin P, resveratrol, phloretin, phlorizin, and caffeic acid were discriminated by using principal component analysis and hierarchical cluster analysis. The present work provides a simple strategy to adjust the ECL wavelength of g-CN and presents a simple way to fabricate multicolor ECL sensing array, which has great application potential for multiplexed analysis and multicolor ECL imaging sensing.