The title complex, {[N(CH3)(4)](2)[Cd(SCN)(2)S]}(n), was prepared by self-assembling from the reaction of a methanol/water (volume ratio, 1/1) solution containing cadmium(II) thiocyanate with equivalent amount of tetramethylammonium thiocyanate. The result of single X-ray determination for the complex reveals that a novel polymeric cadmium(II) complex bridged by sulfur and thiocyanato ions was obtained, which formed a two-dimensional (2D) structure.