The new bulk superconductors of Pr1-xCaxBa2Cu3O1-δ (0.4≤x≤0.6) have been synthesized under high pressure for the first time to our knowledge. The highest Tc of 98K was observed for Oxygen-deficient tetragonal Pr0.5Ca0.5Ba2Cu3O7-δ sample. Our results demonstrate the valence state of Pr in 123 structure is a mixed sate greater than 3+, hole filling and hybridization are the primary cause of the suppression of superconductivity by Pr in 123 structure.