AbstractThe bonding situation in the tricoordinated beryllium phenyl complexes [BePh3]−, [(pyridine)BePh2] and [(trimethylsilyl‐N‐heterocyclic imine)BePh2] is investigated experimentally and computationally. Comparison of the NMR spectroscopic properties of these complexes and of their structural parameters, which were determined by single crystal X‐ray diffraction experiments, indicates the presence of π‐interactions. Topology analysis of the electron density reveals elliptical electron density distributions at the bond critical points and the double bond character of the beryllium‐element bonds is verified by energy decomposition analysis with the combination of natural orbital for chemical valence. The present beryllium‐element bonds are highly polarized and the ligands around the central atom have a strong influence on the degree of π‐delocalization. These results are compared to related triarylboranes.