Thirty-three Chilean corn accessions were screened for the first time regarding their phenolic profiles, total phenolic contents (TPC), antioxidant capacity (DPPH and ABTS), and in vitro inhibition against key enzymes relevant for hyperglycemia (alpha-amylase and alpha-glucosidase) and hypertension (angiotensin I-converting enzyme, ACE-I) in both free and cell wall-bound fractions. TPC varied from 132.2 to 262.5 mg of gallic acid equivalents/100g dry weight (DW), and around 88% of TPC and antioxidant capacity were found in the bound form. Vanillin, vanillic, protocatechuic, ferulic, and p-coumaric acids were detected by HPLC in free fractions, whereas ferulic and p-coumaric acids were found in the bound form. Pisankalla accession (red kernel) had the highest ferulic acid content (269.5 mg/100g DW). No alpha-amylase and ACE-I inhibition were found; however, all free fractions inhibited alpha-glucosidase (10.8-72.5%). Principal component analysis revealed that darker samples (free fraction) showed higher TPC and antioxidant capacity, while alpha-glucosidase inhibition was related to yellow-colored samples.