IntroductionAromatic amines released from azo dyes are regulated in textile products under the European REACH framework due to their potential health risks. Their determination remains analytically challenging because of their structural similarity, moderate polarity, and the complexity of textile matrices, which can cause significant matrix effects.MethodsA green Capillary Electrophoresis method coupled with Diode Array Detection (CE–DAD) was developed for the simultaneous determination of eleven regulated aromatic amines in textile extracts. A Design of Experiments (DoE) approach was employed to systematically optimize the separation conditions, with the aim of maximizing resolution, selectivity, and robustness while minimizing analysis time. The environmental sustainability of the analytical procedure was assessed using the BAGI and Agree metric.ResultsThe optimized CE–DAD method showed satisfactory analytical performance when validated using spiked textile extracts, providing adequate recovery, precision, and robustness. The method also demonstrated good applicability to complex textile matrices. The green assessment confirmed the low environmental impact of the proposed analytical procedure.ConclusionsThe developed CE–DAD method represents a sustainable, reliable, and cost-effective analytical strategy for the simultaneous determination and monitoring of regulated aromatic amines in textile products. The integration of DoE-based optimization and green analytical assessment highlights its potential as an environmentally responsible alternative for analysis of complex textile matrices.