Unlike conventional concrete, the material design process for engineered cementitious composites (ECC) involves micromechanics-based design theory, paving the way for the use of high volumes of fly ash (HVFA) as a major component. Using high volumes of fly ash (up to 85% weight fraction of cement) in ECC mixtures enables improved tensile ductility (approximately a 3% increase in long-term tensile strain) with reduced crack widths, although it also leads to significantly reduced early-age compressive and tensile strength and chloride ion resistance. However, nanomineral additives are known to improve mechanical strength and durability of HVFA systems. The study emphasizes the effects of different fly ash (FA)/cement ratios on various properties (hydration and microstructural characteristics, transport and mechanical properties) of ECC mixtures designed with different mineral additives. Experimental results confirm that although different optimum levels can be selected to favor various ECC properties, optimum weight fraction of FA is dependent on the mechanism of nanomodification (that is, type of modifier). The optimum level of fly ash weight fraction that yields the highest rate of improvement through nanomodification of ECC varies for different mechanical and transport properties.