This Article reveals a rare synthesis of pure Pr2O2CO3 (POC) nanopowder by thermolysis (700 degrees C) of a single chemical precursor in an autogenic reaction. The autogenic thermolysis of praseodymium acetate is a solvent-free, efficient, and straightforward approach yielding luminescent POC nanoparticles. The as-prepared POC nanopowder converted to PrO1.833 (PO) powder via combustion. Methodical morphological, structural, and compositional characterizations of POC and PO powders are carried out, supported by mechanistic elucidation and the photoluminescent properties.