Increasing demands to obtain chemicals via greener and more sustainable materials and processes introduces concepts that should be considered and applied from lab to larger scales. Obtaining bioactive chemicals from agro-industrial non-food biomass waste can combine benign techniques and bio-circular economy to reach this goal. After extraction, evaluating profitability and environmental impacts to decide whether separation - and to what extent - is necessary or not is indispensable. This could be integrated into an approach known as sufficiency, as an important criterion for sustainability. From this perspective, Brazil's annual generation of 8 million tons of orange waste is relevant, since citrus waste has large amounts of highvalue compounds, such as pectin, D-limonene and flavonoids. This case study aimed at developing and comparing green and sustainable analytical methods to obtain flavonoids from orange peel. Homogenizer, ultrasound and microwave-assisted extractions were employed using chemometric tools, considering time, sample/solvent ratio, temperature and ethanol concentration as variables to obtain extracts containing hesperidin, naringenin, hesperetin and nobiletin. The bioactive flavonoids were determined by high-performance liquid chromatography (HPLC-UV). Microwave extraction was the most efficient method for obtaining the majority of flavonoids studied, six times more for hesperidin. Moreover, orange waste from different farming models showed diverse chemical profiles showing the importance of this alternative in natural product resources.