Several benzyl oxalates were converted to the corresponding bibenzyls in good yield by pyrolysis in the gas phase. Since oxalates are readily prepared from benzyl alcohols, pyrolysis of oxalates offers a convenient way of converting benzyl alcohols to bibenzyls. Pyrolyses of the unsymmetrical oxalates, benzyl p-chlorobenzyl oxalate and benzyl benzyl-α,α-d2 oxalate, indicate that the mechanism of the reaction requires statistical scrambling of the benzyl groups, which is consistent with the formation of benzyl radicals. Gas-phase pyrolysis of oxalates appears to be a means of generating relatively stable radicals, such as benzyl radicals, in the absence of any very reactive radicals or molecules. © 1968, American Chemical Society. All rights reserved.