This study introduces a novel method for the quantification of malachite green (MG), a pervasive cationic dye, in surface water by synergizing multiphase electroextraction (MPEE) with digital image analysis (DIA) and partial least square discriminant analysis. Aimed at addressing the limitations of conventional DIA methods in terms of quantitation limits and selectivity, this study achieves a significant breakthrough in the preconcentration of MG using magnesium silicate as a novel sorbent. Demonstrating exceptional processing efficiency, the method allows for the analysis of 10 samples within 20 min, exhibiting remarkable sensitivity and specificity (over 0.95 and 0.90, respectively) across 156 samples in both training and test sets. Notably, the method detects MG at low concentrations (0.2 µg L−1) in complex matrices, highlighting its potential for broader application in environmental monitoring. This approach not only underscores the method's cost‐effectiveness and simplicity but also its precision, making it a valuable tool for the preliminary testing of MG in surface waters. This study underscores the synergy among MPEE, DIA, and chemometric tools, presenting a cost‐efficient and reliable alternative for the sensitive detection of water contaminants.