Nowadays, Green Analytical Chemistry is widely applied to provide various analytical methods with eco‐friendly procedures employing the least toxic, harmful reagents on humans and the environment without affecting the efficacy of the determination. Accordingly, two eco‐friendly, accurate, and reliable high‐performance thin‐layer chromatography‐densitometry and high‐performance liquid chromatographic methods were established for the determination and separation of two antispasmodic drugs, namely phloroglucinol and trimethylphloroglucinol in their pure, combined dosage form along with phloroglucinol toxic impurity, 3,5‐dichloroaniline. For high‐performance thin‐layer chromatography‐densitometry, efficient separation was developed via utilizing the stationary phase of high‐performance thin‐layer chromatography silica gel 60 F254 plates and developing a system comprising of ethyl acetate‐butanol‐ammonia in the ratio of 8.0:2.0:0.2, by volume and scanning of the developed bands at 210.0 nm. The subsequent method is isocratic high‐performance liquid chromatography with diode array detection in which separation was successively attained using XTerra RP‐C18 (250 × 4.6 mm, 5 μm) column as stationary phase and methanol‐10.0 mM phosphate buffer, pH 3.7 ± 0.1 as mobile phase in the ratio of 75.0:25.0, v/v at flow rate 1.0 ml/min and scanning at 220.0 nm. The developed liquid chromatography methods were validated according to the International Council for Harmonization guidelines, and all results acknowledged their efficacy. Additionally, the proposed methods worked well for assessing the cited drugs in binary combined commercially available pharmaceutical formulation. The greenness profile of the present methods was assessed and estimated using various assessment tools, namely; Green Analytical Procedure Index, analytical eco‐scale method, National Environmental Method Index in addition to Analytical GREEnness tool to evaluate the greenness of the provided methods with a statistical comparison between them to assess the more green ones.