The high pavement temperature plays an important role in the development of urban heat island (UHI) in summer. The objective of this study was to develop water retentive and thermal resistant cement concrete (WTCC) to enhance the pavement cooling effects. The WTCC was prepared by combining a water retentive material and a high aluminum refractory aggregate (RA) with porous cement concrete (PCC). Water retention capacity test, fluidity test, and compressive strength test were used to determine the composition ratio of the water retentive material. Mechanical performance and cooling effects of WTCC were evaluated by compressive and flexural strength tests and temperature monitoring test. The mass ratios of fly ash, silica fume, cement, and water in the water retentive material were determined as 65:35:15:63.9. The compressive strength and the flexural strength of WTCC after 28 days curing were 30.4 MPa and 4.6 MPa, respectively. Compared with stone mastic asphalt (SMA) mixture, PCC, and water retentive cement concrete (WCC), surface temperature of WTCC decreased by 11.4 °C, 5.5 °C, and 4.1 °C, respectively, and the internal temperatures of WTCC decreased by 10.3 °C, 6.1 °C, and 4.6 °C, respectively. The water retentive material has benefits of strength improvements and temperature reduction for WTCC. Based on the results, WTCC proved to have superior cooling effects and the potential to efficiently mitigate the UHI effects and be used in medium traffic roads.