A series of silver(I) and gold(I) carbene complexes of the type [M(L)(2,2′‐bipyridine)][PF6] (L = 1‐benzyl‐3‐(2‐pyridylmethyl)benzimidazolylidene; M = Ag (1); M = Au (3)) and [M(L)(carbazole)] (M = Ag (2); M = Au (4)) were synthesized and analyzed using a range of spectroscopic and crystallographic techniques. Inspection of the solid‐state structures of 1, 2 and 4 revealed a number of intermolecular noncovalent interactions. In the solid‐state structure adopted by 1, π–π and Ag–Ag interactions directed the complexes to orient in a head‐to‐tail fashion. The photophysical properties were found to be influenced by the ancillary ligands in solution as well as in the solid‐state. Calculations were performed to support the aforementioned structural and optoelectronic assignments.