Engineered Cementitious Composites (ECC) are highly regarded in construction owing to their tensile ductility and crack control capabilities, making them suitable for various structural applications. The accumulation of multi-walled carbon nanotubes (MWCNTs) further enhances their mechanical properties. However, there’s a significant knowledge gap concerning MWCNTs-ECC impact resistance. The objective of this study is to tackle the challenges associated with evaluating, optimizing, and predicting MWCNTs-ECC impact resistance to ensure its safe and widespread use in critical infrastructure by applying response surface methodology (RSM). Moreover, the 13 mixtures of ECC combined with several quantities of PVA fiber and MWCNTs as input elements were utilized to calculate the first (E1) and final (E2) impact energies. The findings demonstrated that the MWCNTs-ECC combinations’ impact resistance improved as the input ingredient concentrations increased. Besides, the optimum E1 and E2 of ECC combined with 1% of PVA fiber were noted by 1398 Joules and 12,956 Joules at 0.065% of MWCNTs on 28 days respectively. Furthermore, Response prediction models for E1 and E2 were created, and after being validated with an analysis of variance (ANOVA), it was determined that they had high R2 readings of 99.30% and 99.07%, correspondingly. The optimization process produced an ideal number of input variables for MWCNTs and PVA fiber, respectively, of 0.066% and 1%, with a desirability value of 100%. Moreover, it is recommended that the usage of 0.066% of MWCNTs in ECC combined with 1.0–1.50% PVA fiber provides optimum results for the construction industry.