The crystal structures and optoelectronic properties of the compounds 1,4-bis[2-(1-naphthyl)vinyl]benzene (BNVB), 4,4′-bis[2-(1-naphthyl)vinyl]biphenyl (BNVBP) and 4,4′-bis[2-(9-anthryl)vinyl]biphenyl (BAVBP) were studied and compared. Due to intramolecular H⋯H steric hindrance, BAVBP molecules adopt a twisted conformation and constructed into a three-dimensional C–H⋯π interacting structure. In contrast, the H⋯H steric hindrance is alleviated in compounds BNVB and BNVBP. Both molecules have much better planar character and aggregate into a lamellar structure with a herringbone packing motif. The aggregate structure exerts a dramatic influence on the optoelectronic properties. Compound BAVBP shows an aggregation-induced enhanced emission (AIEE) character. While, both BNVB and BNVBP are AIEE-inactive, BNVBP displays moderate hole-transporting ability.