Two new discrete Btz-bridged pentanuclear metal complexes, [HDMF][NaHg4(Btz)6I4] (1) and [Zn5(Btz)6(L)3(Ac)] · 0.5MeOH · 0.5H2O (2) (Btz = deprotonated benzotriazole, L = p-aminobenzoate, HDMF = protonated DMF, and Ac = acetate), were synthesized using three-layered diffusion and natural evaporation methods, respectively. In 1, the pentanuclear anion [NaHg4(Btz)6I4]− is composed of a tetrahedral arrangement of four four-coordinate Hg(II) ions centered on the six-coordinate Na(I), and thereby forming a rare Btz-bridged hetero-metal complex. Compound 2 is a neutral pentanuclear homo-metal complex, consisting of a tetrahedral arrangement of four five-coordinate Zn(II) ions centered on the fifth six-coordinate Zn(II). The thermal stabilities and solid-state photoluminescence of the two complexes have been investigated.