Chiral recognition of amino acids is crucial in pharmaceutical and clinical fields due to the enantiomer-dependent bioactivity of chiral compounds. Here, we report an electrochemiluminescent (ECL) sensor utilizing a chiral covalent organic framework (CC-MP CCTF) for the selective discrimination of phenylalanine (Phe) enantiomers. Critical experimental parameters, including buffer pH (optimized to 7.38), tripropylamine (TPrA) concentration (9.99 mM), and CC-MP CCTF dilution ratio (1.6×), were optimized to maximize sensitivity. The sensor achieved a linear detection range (0.2–1.0 mM) for both D- and L-Phe with a limit of detection (LOD) of 0.1 mM. Remarkably, it exhibited exceptional enantioselectivity, showing a 1.96-fold higher ECL response to D-Phe than L-Phe, which originates from the chiral confinement effect of the CC-MP CCTF. This study proposes a cost-effective and rapid strategy for chiral amino acid recognition, demonstrating potential applications in bioanalysis and quality control processes.