Pr1+xBa2−xCu3O7±δ solid solution was investigated by means of X-ray powder diffraction and Rietveld analysis. Single-phase PrBa2Cu3O7±δ (Pr123) can be synthesized under a Pr-rich condition by sintering at 950 °C in air. The solubility of Pr1+xBa2−xCu3O7±δ solid solution is 0.08≤x≤0.80. The structure of Pr1+xBa2−xCu3O7±δ is orthorhombic for 0.08≤x<0.30, and transforms into tetragonal for 0.30≤x≤0.80. To form single-phase Pr123, the Ba sites in the Pr123 structure are partially occupied by excess Pr ions, and the smallest amount of excess Pr is x=0.08. Meanwhile, all Ba ions stay in the Ba sites.