The Zintl phase Eu₂Si was synthesized from elemental europium and silicon in a sealed tantalum tube in a high‐frequency furnace at 1270 K and subsequent annealing at 970 K. Investigation of the sample by X‐ray powder and single crystal techniques revealed: Co₂Si (anti‐PbCl₂) type, space group Pnma, a=783.0(1), b=504.71(9), c=937.8(1) pm, wR2 = 0.1193, 459 F² values and 20 variables. The structure contains two europium and one silicon site. 151Eu Mössbauer spectroscopic data show a single signal at an isomer shift of −9.63(3) mm/s, compatible with divalent europium. Within the Zintl concept electron counting can be written as (2Eu²⁺)⁴⁺Si⁴⁻, in agreement with the absence of Si‐Si bonding. Each silicon atom has nine europium neighbors in the form of a tri‐capped trigonal prism. The silicon coordinations of the Zintl phases Eu₂Si, Eu₅Si₃, EuSi, and EuSi₂ are compared.