The high-performance liquid chromatographic separation of colchicine and its hydrolysis and photodecomposition products has been investigated. Separation of colchicine, N-desacetyl-colchicine, β- and γ-lumicolchicine can be accomplished by modification of existing methods; however, under these conditions the tropolone derivatives, colchiceine and trimethylcolchicinic acid, do not elute. Based on the observed complexation of tropolone with metal ions, copper(II) ions were incorporated in the eluent enabling the direct detection and quantitation of the tropolone derivatives. Separation of colchicine, isocolchicine and their respective derivatives has been optimised for both phosphate buffer and aq. copper solutions.