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Potent muscle relaxant (thiocolchicoside, TCC) and nonsteroidal anti-inflammatory drug (etoricoxib, ETXB) fixed-dose combination is formulated at relatively high 1:15 and 1:7.5 ratios for TCC and ETXB, respectively. Since the minor component (TCC) has lower absorptivity, assay of TCC/ETXB tablets presents an analytical challenge. The current study presents two novel methods: first is a micellar electrokinetic capillary chromatography (MEKC). Background electrolyte is borate buffer (40 mM, pH 9.2) containing 30 mM sodium dodecyl sulfate and methanol (ratio 80:20%, v/v), measured at 210 nm. Second is a direct double A max spectrophotometric method; minor component, TCC, is measured directly at its distant λ max (373 nm), at zero absorption of ETXB. Then, a ten-fold dilution step is carried out to eliminate TCC spectral interference and ETXB is determined at its λ max (282 nm). Both drugs’ concentrations disclose obedient linearities at 2–100 μg·mL−1 in MEKC, versus 3–25 and 40–350 μg·mL−1 for TCC and ETXB, respectively, in spectrophotometry. All ICH validation elements have been fulfilled for the developed methods. MEKC and spectrophotometric assays achieve accuracy, precision, selectivity, and robustness to be recommended for industrial quality control routine analysis of TCC/ETXB pills formulated at cited ratios or even higher.