The global coatings industry faces mounting pressure to reduce reliance on petroleum-derived, volatile organic compound (VOC)-laden formulations and promote sustainable and innovative, low-toxicity alternatives. This study investigates the production, application, and comprehensive performance evaluation of eco-friendly acrylic emulsion paints formulated from low-cost indigenous raw materials sourced in Nigeria. Three paint formulations (A, B, and C) were systematically developed by partially substituting conventional synthetic extenders with modified cassava starch as modifier and binder, palm kernel shell (PKS) ash as extender and bulk and neem leaf extract as a biocide. Standard physicochemical and performance tests including viscosity, pH, density, fineness of grind, spreading rate, drying time, opacity (contrast ratio), adhesion, scrub resistance, water absorption, VOC content, and heavy metal analysis were conducted in accordance with Nigerian Industrial Standards (NIS), British Standards (BS 3900), and ASTM protocols. Results demonstrated that Formula C, incorporating the highest proportion of bio-based indigenous additives, outperformed commercial-grade paints in scrub resistance (2,430 cycles), adhesion (Grade 0), water resistance, and VOC emission (19 g/L), significantly below the 50 g/L eco-label threshold. Production cost analysis revealed savings of approximately 55–64% compared to equivalent commercial products. The findings confirm that these locally sourced indigenous materials can serve as viable, sustainable, and cost-effective components in green paint synthesis, offering significant economic, environmental, and technological benefits for the Nigerian coating industry and developing economies at large. Keywords: eco-friendly paint; gum arabic acrylic emulsion; green synthesis; indigenous raw materials; cassava starch; palm kernel shell ash; sustainable coatings; low-VOC; biocide.