Currently, food science faces the challenge of finding methods to deliver functional and nutritional compounds in ready-to-eat products. Biopolymeric films enriched with essential oils are an emerging strategy for incorporating valuable components into edible carrier matrices. This study investigated the wastewater from orange peel hydrodistillation as a source of phenolic compounds and an innovative ingredient to develop bioactive limonene-loaded pectin-based films, addressing waste disposal challenges by developing a multi-functional packaging material. The objective was to evaluate the effects of formulation synergies, particularly pectin-phenolic interactions, on the physicochemical, rheological properties, and essential oil retention capacity of film-forming emulsions, and then assess the effects on the physicochemical and mechanical properties of the films. Films were analyzed for morphology, water vapor permeability, light transmittance, mechanical, chemical, and physical properties, and encapsulation efficiency. Three formulations were evaluated: pectin control (PC), pectin with Tween-80 surfactant (PT), and pectin with phenolic-rich wastewater (PPW). PPW emulsions displayed higher viscosity, consistency, kinetic stability, and essential oil retention compared to PC. The resulting environmentally-friendly films exhibited increased thickness, improved oil droplet distribution, a more crystalline structure, lower clarity, better flexibility, and increased water vapor permeability. Altered FTIR spectrum bands suggested potential pectin-phenolic interactions, influencing film physicochemical properties through mechanisms such as enhanced crosslinking. The PT film-forming emulsion demonstrated lower kinetic stability and less homogeneity than PC and PPW, showing that the use of the commercial surfactant (0.1g/100 g of film-forming emulsion) led to less favorable performance in terms of emulsion stability and film properties compared to PPW and PC. Conclusively, utilizing orange residue for bioactive pectin-based films offers valuable insights for promoting shelf life, reducing the need for formulation surfactants, and adding nutritional value in food applications, while simultaneously repurposing underutilized waste. This research also contributes to insights into the development of more stable emulsions for creating uniform films.