Avocado seeds are an agroindustrial residue widely produced in Mexico that are causing various environmental problems due to their accumulation. The evaluation of avocado residues to recover biopolymers by microwave-assisted extraction (MAE) and the characterization of avocado starch properties were studied in the present work. A central-composite design was used to optimize the MAE process. Moreover, a comparison was performed between MAE non-isothermal mode (NO–ISO) and conventional extraction. Starch optimization by MAE was obtained at 161.09 °C for 56.23 min with an extraction yield of 49.52% ± 0.69%, while with NO–ISO at 161 °C was obtained 45.75% ± 2.18%. Conventional extraction was 39.04% ± 2.22%. Compared with conventional starch, MAE starch showed similar proprieties and molecular spectra. In contrast, MAE starch showed high solubility, low water absorption capacity, a non-granular structure with small particle size (<2 µm) and polydispersity of fragments at different sizes of polymers. Therefore, MAE is a viable technology to extract the starch, and avocado seed can be considered an excellent starch source for the development of novel functional foods, contributing to promoting sustainability across the food chain.