Vannamei shrimp shell waste represents a promising renewable resource for sustainable chitosan production in food biopolymer applications. This study aimed to optimize the eco-friendly extraction of chitosan from Vannamei shrimp shell waste using a combination of Averrhoa bilimbi extract and citric acid as natural organic acids during the demineralization process. Response Surface Methodology (RSM) with Central Composite Design (CCD) was employed to evaluate the effects of citric acid concentration and soaking time on ash content reduction. The optimum extraction condition was obtained at 25.260% citric acid concentration and 100.470 minutes soaking time, resulting in chitosan with 7.464% ash content. The optimized chitosan exhibited moisture, protein, lipid, and carbohydrate contents of 11.52%, 0.49%, 0.06%, and 80.45%, respectively, with a moderate degree of deacetylation (65.98%). FTIR analysis confirmed the presence of characteristic chitosan functional groups, including O–H, N–H, C–H, and C–O vibrations, indicating successful deacetylation and chitosan formation. Morphological analysis using Scanning Electron Microscopy (SEM) revealed a porous and interconnected surface structure compared to commercial chitosan. In addition, the optimized chitosan showed lower ash and protein contents than commercial chitosan, indicating effective mineral and protein removal during extraction. These findings demonstrate that natural organic acids can serve as environmentally friendly alternatives to mineral acids for chitosan extraction and highlight their potential application in biodegradable food packaging and edible coating applications.