A general procedure was developed for the synthesis of diarylcalcium complexes by addition of KOtBu to arylcalcium iodides in THF. Intermediate arylcalcium tert‐butanolate dismutates immediately leading to insoluble tert‐butanolate precipitates of calcium. Depending on the steric demand and denticity of additional neutral aliphatic azabases, mononuclear or dinuclear complexes trans‐[Ca(α‐Naph)2(thf)4] (1), [Ca(β‐Naph)2(thf)4] (2), [Ca(Tol)2(tmeda)]2 (3), [Ca(Ph)2(tmeda)]2 (4), [Ca(Ph)2(pmdta)(thf)] (5), [Ca(hmteta)(Ph)2] (6), and [Ca([18]C‐6)(Ph)2] (7) were isolated (Naph=naphthyl; meda=N,N,N′,N′‐tetramethylethylenediamine; pmdta= N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine; hmteta=N,N,N′,N′′,N′′′,N′′′‐hexamethyltriethylenetetramine). The CaC bond lengths vary between 250.8 and 263.5 pm, the ipso‐carbon atoms show low‐field‐shifted resonances in the 13C NMR spectra.