A new one-dimensional (1D) azido-bridged manganese(II) complex, [Mn(dpq)(N3)2]n [dpq=dipyrido-(3,2-d:2′,3′-f)-quinoxaline] (1), was synthesized and characterized. Crystal structure study reveals that 1 contains a 1D manganese(II) chain bridged by alternating double end-to-end (EE) and double end-on (EO) azido ligands. The strong interchain π–π stacking interaction extends the structure into a 2D supramolecular array. The analysis of magnetic data indicates that the EO- and EE-azido bridges mediate the ferromagnetic and antiferromagnetic interactions, respectively. Interestingly, complex 1 exhibits a weak ferromagnetic property below 6K probably due to spin canting.