The complexation of E- and Z-enolborinate E, Z with acetaldehyde R should be proceed via two types: the fisrt, anti-complexation, leading to two types of complexes. The second, syncomplexation, leading only to one type of complexes. In addition, one of two complexes of the anti-complexation have intramolecular hydrogen-bonding between formyl hydrogen on R with oxygen atom on E, Z. The complexes containing intramolecular hydrogen-bonding are the most stables in comparison with the others.