The search of a practical method to analyze cis-diol-containing compounds outside laboratory settings remains a substantial scientific challenge. Herein, a smartphone-based colorimetric reader was coupled with a remote server for rapid on-site analysis of catechols. A smallest-scale 2×2 colorimetric sensor array composed of pH indicators and phenylboronic acid was configured. The array was able to distinguish 13 catechols at 6 serial concentrations, through simultaneous treatment via principal component analysis, hierarchical cluster analysis, and linear discriminant analysis. After both the discriminatory power of the array and the prediction ability of the partial least squares quantitative models were proved to be predominant, the smartphone was coupled to the remote server. All the ΔRGB data were uploaded to the remote server wherein linear discriminant analysis and partial least squares processing modules were established to provide qualitative discrimination and quantitative calculation, respectively, of the analytes in real time. The applicability of this novel method to a real-life scenario was confirmed by the on-site analysis of various catechols from a water sample of the Yangtze River; the feedback result in the smartphone showed the method was able to identify the catechols with 100% accuracy and predict the concentrations to within 0.706-2.240 standard deviation.