In the near future, the key for the civil engineering community will be to accomplish project objectives in line with the concept of sustainable development and energy-saving, which will require the use of high-performance materials manufactured at a fair price with the smallest possible environmental impact. As a novel eco-friendly material, Engineered Cementitious Composite (ECC) offers to solve the problems both of sustainable development and energy saving because of its potent ability to manage crack width, good behaviour of flexural toughness, and improved durability performance. The partial replacement of fly ash for cement in ECC minimizes environmental pollution and conserves natural resources, and is gaining increased attention in the construction practice. This study presents the experimental findings on the influence of high calcium fly ash on the mechanical properties of ECC. By employing micromechanics-based material design under different w/c content from 0.28 to 0.32, ductility in excess of 3% under uniaxial tensile test can be attained, and the multiple micro cracking behaviour response can be achieved. The experimental program also conducted sorptivity and water absorption tests to determine the capillary suction and its capacity. It was indicated from the experiment that the sorptivity rate off ECC considered by the initial cracking had no relation with w/c (water to cement) ratio using high calcium fly ash. Furthermore, rapid chloride penetration and chloride diffusion also added to corroborate findings. The result for all mixtures satisfied low chloride ion penetrability levels in accordance with ASTM C1202.