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Food by-products containing bioactive substances, such as phenolic compounds, have garnered attention due to the possibility to increase the value of what would otherwise be considered residue. The present work sought to evaluate the extraction of phenolic compounds and their bioaccessibility from pinhao “comum” (Araucaria angustifolia var. angustifolia) and pinhao “macaco” (Araucaria angustifolia var. indehiscens) cooking water extracts during in vitro simulated gastrointestinal conditions. Our findings indicate that changes occurred depending on the type of extract and the gastrointestinal step. Although both of the evaluated pinhao extracts displayed bioaccessible phenolic compounds, the gradual bioaccessibility decrease of pinhao “macaco” extract during in vitro simulated gastrointestinal condition steps, characterizes this extract as the one with the best functional property. The functional property is related to antioxidant properties which are able to generate protective effects against various diseases.