The recent progress in experimental and theoretical study of the alkali‐group IIB intermetallic excimers will be summarized. The main concern here is an understanding of interatomic interaction and collision dynamic in intermetallic systems. In the experiments, intermetallic vapors of amalgams are illuminated by a pulsed laser radiation. The reactive and non reactive energy transfer processes occur in the vapor or plasma, resulting with emission of the excited atoms and molecules. The analysis of the emission show a complexity of vapor and plasma conditions.Appropriate vapor mixture preparation, exciting laser wavelength selection and temporal spectral analysis allow discrimination among different collision processes. The photochemical reaction of excited alkali dimer with group IIB atoms, photoassociation of alkali and IIB atoms, quasi resonant and resonant alkali atom excitation with subsequent energy transfer to IIB atoms, are illustrated for Li‐Zn and Li‐Cd systems. Accompanying theoretical work provides interatomic potential energy curves necessary for interpretation of the observed emission. The emphasis is made on proper treatment of spin‐orbit interaction which increases from Zn towards Hg. Recent calculation of potential energy surfaces for the Li2Zn system shows that exciplex can be formed in the excited state with considerable binding energy.