This study aims at evaluating the effect of ultrafine granulated copper slag (UGCS) on hydration development of blended cement and mechanical properties of mortars. The UGCS with the median particle size of 4.78 μm and BET surface area of 1.31 m²/g was used as a cement replacement to prepare blended cements. Hydration heat emission of blended cement and mechanical performance of mortars were investigated by using isothermal calorimetry and strength tests, respectively. X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were applied to the analysis of pozzolanic reaction and hydration products. The results illustrate that UGCS has influence on the hydration heat evolution of blended cement due to its filler effect and pozzolanic reaction. The cumulative hydration heat of blended cement is reduced by partial cement replacement with UGCS. The test mortar prepared by using blended cements with 30 wt. % UGCS shows a retardation of strength development with a low value at early ages (7 days) and a rapid growth at later ages (28 days). The 90-day compressive strength of test mortar is 45.0 MPa close to that of the control mortar (49.5 MPa). The obtained results from XRD and TGA analysis exhibit an increase in calcium hydroxide (CH) consumption and calcium silicate hydrates (C–S–H) formation in blended cement pastes with curing time. The cement replacement with UGCS induces changes in microstructure of blended cement paste and chemical composition of hydration products.