•New fluorescence dyes based on triphenylpyridine were synthesized.•Compounds exhibited efficient emission from blue to green with high quantum yields.•HOMO/LUMO energy levels were obtained by CV and theoretical calculation.•The effects of solvents on the fluorescence characteristics were investigated.•All of the compounds possess of suited HOMO ranges (−5.56 to −5.70 eV).A series of novel triphenylpyridine-containing triphenylamine derivatives have been carefully designed and prepared in good yields using the stepwise route reactions. The relationship of photoluminescence property and structure of compounds 9–13 was systematically investigated via UV–vis, fluorescence, thermogravimetric and electrochemical analyzer. The highest occupied molecular orbital and the lowest unoccupied molecular orbital distributions of compounds 9–13 were calculated by density functional theory method. The high fluorescence quantum yields, desirable the highest occupied molecular orbital levels and high thermal stability of compounds 9–13 indicate that the linkage of triphenylpyridine and triphenylamine is an efficient means to enhance hole-transporting ability and fluorescent quantum yield.Graphical abstractNew framework triphenylpyridine derivatives containing triphenylamine groups were synthesized and the relationship of photoluminescence property and structure were investigated. Quantum chemical calculations were used to obtain optimized ground-state geometry, spatial distributions of the HOMO, LUMO levels of the compounds.