Despite the great progress in alkali developing photocurable resins for electronic packaging, the continuous development of high-frequency communication technology still poses a great challenge to the high heat resistance, toughness, robustness, and dielectric properties of photocurable resins. In this paper, a simple and feasible method is proposed to prepare a series of naphthalene-based photocurable resins with excellent thermal/mechanical properties and performance by introducing four selected fluorodiamine molecules into 1,6-naphthalene diglycidyl ether (NDE), respectively, and employing maleic anhydride (MA) as the alkali developing functional component. Among them, the effects of MA on the photocuring kinetics and thermo-mechanical properties of the resins were systematically investigated. Most importantly, the high functionality molecules obtained by diamine chain extension effectively improved the properties of the photocured films. As a result, two of the cured films exhibited excellent toughness (3.00 ± 1.39 MJ cm−3 and 4.55 ± 1.16 MJ cm−3), excellent heat resistance (212 and 195 °C), low dielectric constants (2.84 and 3.25), and low dielectric losses (0.0024 and 0.0068). Finally, the fast alkali development capability possessed by these two resins was verified, demonstrating their potential for technical application in real packaging boards and providing an effective strategy for the design and manufacture of high-performance naphthalene-based inks.