The ability to synthesize two-dimensional inorganic nanomaterials is one of the many important challenges in materials science. Olivine LiMPO4 (M = Mn, Fe, Co, Ni) compounds represent an emerging class of cathode materials for lithium-ion batteries, whose electrochemical properties can be significantly enhanced by nano-structuring in two dimensions. My research focuses on developing and understanding synthetic routes that ultimately produce freestanding nanosheets of LiMnPO4. To achieve these goals, my synthetic strategy utilizes Mn3(PO4)23H2O nanosheets as reactive synthons. In chapter 2, I discuss how this approach led to the synthesis of a new Mn3(PO4)2 polymorpha microporous open-framework compound with intriguing potential in emerging electrode applications. In chapter 3, I describe the solvothermal reaction parameters that lead to <10 nm thick nanosheets of LiMnPO4, and how the morphology can be tuned by varying certain factors. Finally, in chapter 4, I discuss the unique nanoscrolling behavior of Mn3(PO4)23H2O nanosheets under specific reaction conditions.