Chilean maize biodiversity may represent a potential source of important bioactive compounds with still unknown health-relevant functional properties. The objective of current research was to study the functionality of 33 Chilean native maize accessions corresponding to 14 local races, through the screening of their phenolic profiles in both the free and cell wall-bound fractions, their total phenolic contents (TPC), the antioxidant capacity by the DPPH and ABTS methods and the in vitro inhibitory activities against key enzymes relevant for hyperglycemia and hypertension management. Maize color was measured through the CIELAB parameters and Principal Component Analysis (PCA) was applied as a statistical tool for revealing relations among evaluated variables. TPC varied from 132.2 to 262.5 mg gallic acid equivalents/100g dry weight (DW) and around 88% of maize phenolic compounds were found in the bound fraction. This fraction also showed higher antioxidant capacities when compared to free forms. Vanillin, vanillic and protocatechuic acids were detected by HPLC in free fractions whereas major phenolic acids in the bound form were ferulic and p-coumaric acids. Pisankalla accession (red kernel) had the highest ferulic acid content (269.5 mg/100g DW). No α-amylase and angiotensin I-converting enzyme (ACE-I) inhibitory activities relevant for hyperglycemia and hypertension, respectively were found. However, all free fractions inhibited the hyperglycemia-relevant α-glucosidase (11-73%). PCA revealed that darker samples (free fraction) showed higher TPC and antioxidant capacities whereas α-glucosidase inhibition was related to yellow-colored samples. Chilean maize accessions show potential as natural sources of phenolic acids with antioxidant capacity and in vitro antihyperglycemia properties.