Whereas Wolff rearrangement of indole-2-diazoketone (1) in the presence of silver benzoate led to the indolyl-2-acetic esters 2a and b in low yields, the reaction of 1 in methanol with copper powder or with acidic resin gave methoxymethyl-2-indolyl ketone (3) in 65–80% yields. Chloromethyl 2-indolyl ketone (4) was prepared and converted to the α-aminoketone hydrochloride salts 5a and b. Treatment of 1 with cuprous iodide in acetonitrile–methanol gave 2a, iodomethyl 2-indolyl ketone (6), and methyl 2-indolyl-glyoxalate (7). Compound 6 was converted to N-(2-(2-indolyl)-2-oxoethyl)pyridinium iodide (8) and to 2-acetylindole (9) while 7 was degraded via indole-2-glyoxylic acid (10) to indole-2-carboxylic acid (11). Compound 7 represents a type of product not previously observed in diazoketone chemistry. The mechanism of its formation is discussed.