AbstractA pair of novel polymorphic ionic cocrystals of 3,4‐dicyanotelluradiazole and tetraphenylphosphonium bromide are synthesized and are characterized by single‐crystal XRD. Strong and directional non‐covalent chalcogen bonds (ChB) between Te and Br are analyzed via solid‐state NMR to reveal large and anisotropic J(¹²⁵Te,^79/81Br) coupling tensors, providing unequivocal evidence for non‐Fermi contact contributions across ChBs. Along with large ^79/81Br quadrupolar couplings for the Br⁻ anions, these data provide new tools to characterize chalcogen bonds and to differentiate between ChB polymorphs.