Reactions of hydrated rare earth nitrates with formamide under mild solvothermal reaction conditions give three different rare earth formate structure types Ln(HCOO)3, Ln(HCOO)3·(HCONH2)2, and [CH(NH2)2][Ln(HCOO)4]. The conditions for the formation of a specific structure type were determined as a function of the size of the rare earth cation, the reaction time, and the reaction temperature. Thirteen previously unreported rare earth formates were obtained; nine were isostructural compounds with the composition Ln(HCOO)3·(HCONH2)2 (denoted by LnFA, Ln = Y (1Y), Sm (2Sm), Eu (3Eu), Gd (4Gd), Tb (5Tb), Ho (6Ho), Tm (7Tm), Yb (8Yb), and Lu (9Lu)), and four were isostructural compounds with the composition [CH(NH2)2][Ln(HCOO)4] (denoted by LnFMD, Ln = Sm (10Sm), Ho (11Ho), Tm (12Tm), and Lu (13Lu)). All compounds contain metal ions that are eight coordinated by oxygen atoms and are connected by anti–anti bridging formato ligands to form frameworks. The coordination geometry is bisdisphenoid in LnFA and square antiprismatic in LnFMD. In contrast, the larger rare earth ions that adopt the Ln(HCOO)3 structure are nine coordinated by oxygen atoms in tricapped trigonal prismatic coordination geometry. The luminescence properties of 2Sm, 3Eu, 5Tb, and 10Sm were investigated by solid state photoluminescence spectroscopy in the range of 300–800 nm. Rare earth oxides were also found to react directly with formamide in the presence of a small amount of water to give the same compositions suggesting that the reaction chemistry can provide a basis for a process to recover rare earth metals from end-of-life products containing oxides such as the phosphors used in fluorescent light bulbs. This possibility was demonstrated by crystallizing rare earth formates starting with a commercially available trichromatic phosphor.