The title compounds, Methyl N-(4-methoxyphenylmethyl)-N′-cyanocarbamimidothioate, I, and Methyl N-[1-(phenylmethyl)-4-piperidinyl]-N′-cyanocarbamimidothioate, II, have been designed and synthesized for use as new potential organic molecular electronic materials. The crystal structure of I and II were determined with crystal data (I: Monoclinic, P21/c, a = 4.746(2) A, b = 5.737(3) A, c = 17.399(7) A, β = 91.667(7)o, R all = 0.0703; II: Orthorhombic, Pna21, a = 18.209(8) A, b = 11.463(5) A, c = 7.539(3) A, β = 90.00 o, R all = 0.0481). N–H···N hydrogen bonds were responsible for the formation of one-dimensional zigzag molecular chains of I, and trifurcated hydrogen-bonded molecular chains were indicated in structure of II. C–H···π and C–H···N hydrogen bonds were found in both structures. All these types of interaction together form an extended three-dimensional network and stabilize the title crystals. Two N′-cyanocarbamimidothioates, which were designed and synthesized for use as a new potential organic molecular electronic materials, have been characterized by X-ray diffraction.