UV-curing　low　dielectric　materials　exhibit　wide　applications　in　the　field　of　additive　manufacturing　of　electronic　packaging,　owing　to　their　environmental　protection,　good　thermal　stability,　low　dielectric　constant　(Dk),　and　dielectric　loss　(Df).　Wherein,　one-step　UV　curing　realizes　process　simplification　of　low　dielectric　materials　gradually　sparked　widespread　research.　In　this　work,　a　series　of　novel　naphthalene-based　low　dielectric　materials　were　prepared　for　one-step　UV　curing.　The　double　bond　conversion　rate　of　resins　exceeds　90　%　in　a　short　time　and　the　resins　perform　exceptional　dielectric　properties　(Dk　＜　2.8,　Df　＜　0.009,　110　MHz),　high　thermal　stability　(T5%　＞　270　°C),　and　hydrophobicity　(water　contact　angle　＞　95°).　Notably,　1,6-naphthalene　dimethacrylate/Trihydroxymethylbutyl　trimethylacrylate　(1,6-NEA/TMPTA)　suggests　lowest　dielectric　performance　(Dk　=　2.19,　Df　=　0.005)　with　significant　thermal　stability　(Tg　=　190　°C,　T5%　=　367.4　°C)　because　the　π-π　conjugation　of　the　asymmetric　structure　of　1,6-NEA,　which　allows　for　a　greater　variety　of　stacking　patterns　and　increases　the　effective　collisions　between　the　reactive　sites　of　the　photosensitive　monomer　and　the　reactive　diluent.　This　work　has　revealed　the　structure-activity　relationship　between　the　substituents　on　naphthalene　derivatives　and　their　photochemical　properties,　providing　a　novel　methodology　for　the　development　of　low　dielectric　electronic　packaging　materials　through　additive　manufacturing　techniques.　©　2024　Elsevier　B.V.