The computer-aided design/computer-aided manufacturing (CAD/CAM) fabrication technique has become one of the hottest topics in the dental field. This technology can be applied to fixed partial dentures, removable dentures, and implant prostheses. This study aimed to evaluate the feasibility of NaCaPO4-blended zirconia as a new CAD/CAM material. Eleven different proportional samples of zirconia and NaCaPO4 (xZyN) were prepared and characterized by X-ray diffractometry (XRD) and Vickers microhardness, and the milling property of these new samples was tested via a digital optical microscope. After calcination at 950 °C for 4 h, XRD results showed that the intensity of tetragonal ZrO2 gradually decreased with an increase in the content of NaCaPO4. Furthermore, with the increase in NaCaPO4 content, the sintering became more obvious, which improved the densification of the sintered body and reduced its porosity. Specimens went through milling by a computer numerical control (CNC) machine, and the marginal integrity revealed that being sintered at 1350 °C was better than being sintered at 950 °C. Moreover, 7Z3N showed better marginal fit than that of 6Z4N among thirty-six samples when sintered at 1350 °C (p < 0.05). The milling test results revealed that 7Z3N could be a new CAD/CAM material for dental restoration use in the future.