The aim of the present study was to extract starch from acorn (Quercus suber L.) fruits using water and alkaline methods. Structural and functional properties of extracted starches were investigated and compared to those of corn and modified starches in order to determine their innovative potential application in food industry. The yield of extraction using the two methods was about 48.32% and 48.1%. The isolated starches showed low moisture, fat and protein contents, revealing high purity and quality. Additionally, the starch extracted using the alkaline method (AAS) showed higher lightness (60.41) when compared to starch isolated using hot water (WAS). However, the lightest white color was found for studied commercial starches. Moreover, AAS starch exhibited the highest swelling power, solubility and water absorption, followed by WAS and commercial starches. Results showed that extracted acorn starches were characterized by greater enthalpy and gelatinization temperatures. Similar observations were noted using FT-IR spectra analysis for all analyzed starches. In addition, granule starches observed using scanning electron microscopy were found to be spherical and ovoid. However, from the analysis by X-ray diffraction, a crystalline pattern of C-type was found for acorn starches, while commercial starches presented an A-type pattern. As an innovative food application, these underexploited acorn starches were valued and served to produce new custards with improved functional properties and better microstructure when compared to commercial custard.