We have developed two novel, isomeric compounds of phenyl-substituted dinaphtho[ 2,3-b: 2', 3'-d] furan (Ph-DNF-VW and Ph-DNF-VV) using a facile synthetic protocol. Notably, Ph-DNF-VW has been shown to be a strong candidate for lightemitting device applications: it forms a herringbone-packing structure with effective C-H center dot center dot center dot pi interactions between phenyl moieties, and exhibits a high thermal stability in the crystal phase in air and a high fluorescence quantum yield in the solid state. Additionally, its carrier mobility is comparable to that of amorphous silicon.