The radioactive metabolites excreted in the urine and faeces after administration of riboflavin‐214C to rats were investigated. Paper chromatography (n‐butanol:acetic acid:water 4:1:5) of urine indicated the presence of five radioactive metabolites. The average Rf‐values were 0.10, 0.20, 0.42, 0.53 and 0.63 respectively. Incubation of urine with urease indicated the presence of minute amounts of radioactive urea. The faeces contained two of the metabolites found in the urine. Metabolite Rf 0.63 was identified as lumichrome. The significance of its predominance in the faeces is discussed. Apart from the metabolite Rf 0.53, the excitation spectrum of which is presented, the metabolites did not fluoresce in an aqueous medium. They were more soluble in water than riboflavin. On a Sephadex G‐25 column they were eluted more rapidly than riboflavin. Hydrolysis experiments showed that none of the metabolites were conjugates of riboflavin.