A spectrodensitometric method is described for the determination of the components of two analgesic mixtures. For the first mixture (paracetamol-ascorbic acid-caffeine-phenylephrine), the pharmaceutically active components were separated from each other and closely related degradation products and impurities on high-performance thin-layer chromatography (F254) plates using methylene chloride-ethyl acetate-ethanol-formic acid (3.5 + 2 + 4 + 0.5) and methylene chloride-ethyl acetate-ethanol (5 + 5 + 1) as the developing systems. The other mixture (phenazone-phenacetin-caffeine) was separated efficiently from the degradation products using the same plates and acetonitrile-chloroform (1 + 1) as the mobile phase. The proposed method was used to determine these mixtures in commercial tablets.