Two new organically templated layered copper(l) sulfites, namely, {H(2)PiP}{Cu-3(CN)(3)(SO3)}(1) and {H(2)PiP}- NaCu2(SO3)2Br(H2O)center dot 2H(2)O (2) (pip = piperazine), have been synthesized by hydrothermal reactions of copper(1) cyanide or copper(l) bromide with NaHSO3 and piperazine. Both compounds exhibit a layered structure. The 2D layer of { Cu-3(CN)(3)(SO3)(2-) in 1 is composed of 1 D chains of copper(l) cyanide interconnected by sulfite anions via both Cu-S and Cu-O bonds, whereas the 2D layer of {NaCu2(SO3)(2)Br2- in 2 is formed by 1D chains of copper(l) bromide and 1D sodium(l) aqua chains that are interconnected by sulfite anions via Na-O, Cu-S, and Cu-O bonds. Chemical bonding in 1 and 2 has been also investigated by theoretical calculations based on DFT methods.