Results of the joint experimental and computational studies of structural features, bonding, and thermodynamic properties of molecular complexes of iodine monobromide with bidentate nonchelating N-containing donors, pyrazine (pyz), 4,4′-bipyridine (bipy), and 1,2-bis(4-pyridyl)ethane (bpa) are reported. Comparison of structural, energetic, and electronic properties reveals that the Lewis basicity with respect to IBr increases in the order pyz < bipy < bpa, while Lewis acidity with respect to pyz increases in the order I2< IBr < ICl. Stabilization of IBr by complexation with bidentate nonchelating Lewis bases allows to recommend (IBr)2·L complexes as a convenient source of IBr.