We report two cationic silver‐based coordination polymers with N‐donating quinoxaline as the linker. [Ag(quinoxaline)+] [–O3S(CH2)2SO3–]0.5·2H2O (which we denote as SLUG‐37 for University of California, Santa Cruz, structure No. 37; quinoxaline = C8H6N2) and [Ag(quinoxaline)+][CH3CO2–] (SLUG‐38) were solved by single‐crystal X‐ray diffraction and further characterized by several solid‐state techniques. Both structures consist of cationic 1D Ag‐quinoxaline chains arranged into π‐stacked layers, with charge‐balancing anions residing in the interlamellar space. The materials can be synthesized hydrothermally as well as in higher yield by reflux or room temperature conditions. The luminescent behavior of SLUG‐37 exhibits a strong white emission making it potentially useful as white LEDs.