To establish accurate and efficient quality control standards for the purity of 1，3，5-trichloro-2，4，6-trinitrobenzene （TCTNB）， the comprehensive performance of the classical acid-base titration method and a newly developed green liquid chromatography method was systematically compared. The acid-base titration method quantifies TCTNB by hydrolyzing it with sodium hydroxide followed by back-titration of the excess base. The liquid chromatography method innovatively employed low-toxicity methanol instead of traditional toxic solvents and achieved baseline separation of the target compound from impurities on a C18 column. Experimental results indicated that the titration method was cumbersome （requiring 5.9 hours per analysis） and exhibited significant inaccuracy， showing a mean measured value of 93.89% with a substantial systematic negative bias of -6.05% compared to the sample''s nominal value. In contrast， the liquid chromatography method demonstrated higher efficiency （requiring 3.2 hours per analysis）， good precision （with a relative standard deviation <0.30%， n=6）， and excellent accuracy， showing a mean value of 99.82% that closely matched the nominal value of 99.94%. The substantial systematic error in the titration method was primarily attributed to the deep color of the hydrolyzed solution， which introduced subjectivity in endpoint determination， and potentially incomplete hydrolysis or interfering side reactions. The liquid chromatography method effectively overcame these limitations due to its superior separation selectivity and detection stability. The newly established liquid chromatography method significantly outperforms the traditional titration method in terms of accuracy， precision， efficiency， and green safety.