A hydrothermal reaction leads to the formation of a novel erbium–mercury compound [Er(IA)3(H3O)(H2O)] n(0.5 nHg2I6) (1) (HIA = isonicotinic acid). The compound has been characterized by single-crystal X-ray diffraction. It is characteristic of a one-dimensional chain-like structure and a two-dimensional supramolecular layer. A solid-state photoluminescence experiment reveals that this compound displays upconversion green photoluminescence. The photoluminescence emission peaks can be attributed to the 4 G11/2 → 4 I15/2, 4 F7/2 → 4 I15/2, and 2 H11/2 → 4 I15/2 of the Er3+ ions. The energy transfer mechanism is consistent with the energy-level diagrams of the erbium ions and isonicotinic acid ligand. This compound possesses Commission Internationale de I'Éclairage chromaticity coordinates of 0.1755 and 0.5213. A solid-state diffuse reflectance measurement reveals that this compound features a narrow optical band gap of 1.97 eV.