White analytical chemistry is a novel concept for the assessment of analytical methods on basis of its validation efficiency, greenness power and economical efficiency. White analytical chemistry-driven stability indicating chromatographic method has been developed for the concomitant analysis of thiocolchicoside and aceclofenac. The proposed chromatographic method has been developed using a safe and environmental-friendly organic solvent for the concomitant stability study of thiocolchicoside and aceclofenac. The analytical risk assessment was carried out for the identification of high-risk analytical risk factors and analytical method performance attributes. The mixture design was applied for the design of experiments-based response surface modelling of high-risk analytical risk factors and analytical method performance attributes. The degradation products were isolated and characterized using infra-red, nuclear magnetic resonance and mass spectral data. The proposed method was compared for its validation efficiency, greenness power and cost-efficiency with published chromatographic methods using the red, green and blue models. The white score of the proposed and reported method was calculated by averaging the red, blue and green scores of the methods. The proposed method was found to be robust, green and economical for the concomitant stability study of thiocolchicoside and aceclofenac. This article is protected by copyright. All rights reserved.