Since the discovery of cuprate superconductors, PrBa2Cu3O7 (Pr123) has attracted much attention due to its nonsuperconductivity and other anomalies. The very recent reports on superconducting Pr123 instead of putting an end of this issue, virtually stimulate more controversies. One of the proposed explanations for the recently observed superconductivity in Pr123 is that the samples could be Ba-rich Pr123 to investigate this possibility, we prepared Pr1-xBa2+xCu3O7 (x=1~0.3) and Pr1-xCaxBa2Cu3O7 (x=0~0.6) as comparison. X-ray absorption near edge spectroscopy (XANES) indicates an increase in carrier concentration with Ba and Ca doping, which is consistent with resistivity and thermoelectric power(TEP) data. However, carriers are introduced in a peculiar why rather than simply add into CuO2 plane.