Thermolysis of copper (II) complex of tryptophan in various solvents led to the formation of tryptamine and indole as a by-product. Similar treatment of copper (II) complex of 1, 2, 3, 4-tetrahydro-1-methyl-β-carboline-3-carboxylic acid (V) afforded harman (VII) which would be formed by air-oxidation of 1, 2, 3, 4-tetrahydroharman (VI). Thermolysis of I and V with copper powder as a catalyst or without catalyst was also examined.