Monomers 3a-3c were prepared from dichlorodicyanopyrazine and aryl-or alkylamines in two steps. Polymerization of monomers 3a and 3b afforded insoluble black solids 4a and 4b, while no solid was obtained from 3c indicating that 3,5-di-tert-butylphenyl groups were too bulky to polymerize. The consumption of cyano groups and the formation of Zn TPyzPz moieties were confirmed by IR spectra and solid-state 13 C NMR spectra. The formation of partially ordered polymers was supported by PXRD measurements. Differences in thermal stability, possibly due to the 2D and 3D network structures, were observed in TG-DTA measurements. The extension of π-conjugation through polymerization and the porous properties of the 4a and 4b were confirmed by diffuse reflectance spectroscopies and adsorption-desorption measurements, respectively. This work demonstrated the novel strategy for the synthesis of 3D FANs to create optically unique and porous organic materials.