With the increasing cement demand for concrete production, this study aims to optimize the compressive strength and rapid chloride permeability (RCP) of high-performance green concrete (HPGC) with minimum cement content using an experimental and analytical response surface method (RSM). Waste palm oil fuel ash (POFA) was treated by heating and grinding processes to produce ultrafine POFA (UPOFA), which employed by 0%, 30%, and 60% as a replacement binder with cement in HPGC production. Silica Fume (SF) was replaced by 0%, 10, 15, and 20% of the remaining mass of cement. The RSM with a central composite design (CCD) approach was utilized to optimize the mix design parameters. The experimental results showed the HPGC containing 30% UPOFA and 20% SF achieved superior compressive strength at ages 28 and 90 days. While 60% UPOFA and 20% SF recorded the lowest chloride permeability. The developed models had statistical significance and demonstrated a satisfactory correlation value (R2) of 99.43 and 99.9; 99.46 and 99.67 for compressive and RCP at 28 and 90 days, respectively. Thus, RSM could be an effective strategy for optimizing the mix design and reducing the harmful environment by minimizing waste volume and intensive energy for cement production, which harnesses concrete sustainability.