The study of the side products of the anodic dissolution of molybdenum and tungsten metals in alcohols in the presence of LiCl showed them to be [LiMo₂O₂(OMe)₇(MeOH)] 1 in the case of MeOH and [LiMo₂O₄(OEt)₅(EtOH)] 2 in EtOH. Treatment of 2 with an excess of PrⁱOH gave [LiMo₂O₄(OPrⁱ)₅(PrⁱOH)] 3, the structure of which was confirmed by a study of [{LiMo₂O₄(OPrⁱ)₄(OC₂H₄OMe)}₂] 4, the product of partial substitution of OR groups in 3 by 2-methoxyethoxide ligands. Reaction of 2 with an excess of MeOC₂H₄OH led to an equimolar mixture of [MoO₂(OC₂H₄OMe)₂] and [LiMoO₂(OC₂H₄OMe)₃] 5. In PrⁱOH a crystalline product identified as [Mo₆O₁₀(OPrⁱ)₁₂] 6 was isolated. Anodic oxidation of tungsten in MeOH gave a mixture of homometallic W(OMe)₆ and [WO(OMe)₄]. Electrosynthesis in EtOH gave as major product an amorphous glass-like mass {after separation of crystalline [WO(OEt)₄] by filtration and subsequent drying of the filtrate in vacuo}. Treatment of the latter with an excess of HOC₂H₄OMe led to crystallization of [{LiWO₂(OC₂H₄OMe)₃}₂· 2Li(HOC₂H₄OMe)₂]²⁺[W₆O₁₉]^2– 7. Complexes 1, 4 and 7 were characterized by X-ray single-crystal studies. A GLC-mass spectrometric study of the composition of organic side products indicated that the processes were associated with formation of ethers, alkyl halides, aldehydes or ketones and their derivatives. The nature of the possible side reactions was deduced on the basis of the data obtained.