The reuse of fruit and vegetable residue (FVR) flour is an alternative to add value to this by-product. FVR features a complex matrix, and the chemical knowledge of the structural interactions of their components might enable the improvement in applications of this residue. This study aimed to evaluate the chemical changes that occur in structure of the FVR flour after different extraction processes. The FVR is the residue of the processing of whole fruits and vegetables several: orange, passion fruit, watermelon, lettuce, courgette, carrot, spinach, mint, taro, cucumber and rocket. The residues of the FVR were analyzed after the extraction with the following extractors: water; pH 7 buffer; pH 9 buffer and FVR defatted by Soxhlet. Residues FVR were analyzed by scanning electron microscope (SEM) at 15kV, 100-4000×-magnification. Sorption isotherm was generating by AquaLab-VSA analyzer at 25°C. FVR flour showed high contents of available carbohydrates (53%), insoluble dietary fiber (38.8%) and significant contents soluble dietary fiber (9.5%) and protein (9.5%). Micrographs FVR flour showed compact and rigid structures, with possibly characteristic fibers, carbohydrates and polysaccharides of the cell wall of fruits and vegetables. The extractors showed different actions on the cell wall of residue, observed by structures characteristics of each sample. As strong interactions promoted that the breaking of cell wall structure forming organized structures hollow circles leaving more exposed other compounds (pH 9 buffer). Adsorption and desorption isotherm confirmed the differences in the residues especially due to the interaction of water with other components of the samples. Therefore the results of the SEM and of sorption isotherms helped in the investigation of changes in the chemical structure of the FVR residue, allowing deepen the knowledge the differences in residues favoring its application to the extraction process, to obtain bioactive compounds or in technological processes.