The photoionization and photodissociation of 1,4-dioxane have been investigated with a reflectron time-of-flight photoionization mass spectrometry and a tunable vacuum ultraviolet synchrotron radiation in the energy region of 8.0-15.5 eV. Parent ion and fragment ions at m/z 88, 87, 58, 57, 45, 44, 43, 41, 31, 30, 29, 28 and 15 are detected under supersonic conditions. The ionization energy of DX as well as the appearance energies of its fragment ions C4H7O2+, C3H6O+, C3H5O+, C2H5O+, C2H4O+, C2H3O+, C3H5+, CH3O+, C2H6+, C2H5+/CHO+, C2H4+ and CH3+ was determined from their photoionization efficiency curves. The optimized structures for the neutrals, cations, transition states and intermediates related to photodissociation of DX are characterized at the B3LYP/6-31+G(d,p) level and their energies are obtained by G3B3 method. Possible dissociative channels of the DX are proposed based on comparison of experimental AE values and theoretical predicted ones. Intramolecular hydrogen migrations are found to be the dominant processes in most of the fragmentation pathways of 1,4-dioxane.