The title compound, 1-4-(dimethylamino)benzylidene)-4-(naphthalene-1-yl) thiosemicarbazide (DMABNTS, C20H20N4S, Mr = 348.47), was synthesized and characterized by elemental analysis, IR, 1H NMR and MS. The crystal structure of DMABNTS with 1,4-dioxane by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c with a = 14.418(4), b = 7.1702(19), c = 28.350(7) (A),β = 101.154(6)°, V= 2875.4(13) (A)3, Z= 4, Dc= 1.212 g/cm3, F(000) = 1120 and μ = 0.151 mm-1. A total of 6458 reflections were collected, of which 4671 were unique. The structure was solved by direct methods and refined to the final R =0.0732 and wR = 0.2127 for 3921 observed reflections (I ＞ 2σ(I)).There exist intermolecular hydrogen bonds (N(2)-H(2B)…S(1A)and N(1)-H(1A)…O(4B)) in the structure. The study of fluorescent properties shows that DMABNTS emits bright solid-state fluorescence in the visible region and exhibits blue photoluminescence.