This report describes the solid-state structures of a series of divinylzinc complexes, one of which represents the only structurally characterized zinc(II) pi-complex. Vinylzinc reagents, Zn[C(Me)=CH2](2) (1) and Zn[C(H)=CMe2](2) (2), have been synthesized and isolated as white crystalline solids in 66 and 72% yield, respectively. Each compound exhibits an infinite polymeric architecture in the solid state via a series of zinc-pi (1) and zinc-sigma-bonded (2) bridging interactions. Addition of chelating ligands to these divinylzinc compounds allowed isolation of the monomeric adducts (bipy)Zn[C(Me)=CH2](2) (1(.)bipy), (tmeda)Zn[C(Me)= CH2](2) (1(.)tmeda), (bipy)Zn[C(H)=CMe2](2) (2(.)bipy), and (tmeda)Zn[C(H)=CMe2](2) (2(.)tmeda), of which 1(.)obipy, 2(.)bipy, and 2(.)tmeda have been characterized crystallographically.