The preparation and characterization of zinc complexes supported by potentially tridentate biphenolate phosphane ligands are reported. The in situ prepared dilithium complexes of 2,2′-tert-butylphosphanylbis(4,6-di-tert-butylphenolate) ([LtBu]2–) and 2,2′-phenylphosphanylbis(4,6-di-tert-butylphenolate) ([LPh]2–) react with ZnCl2 in tetrahydrofuran (THF) to produce lithium zincates Zn[LtBuLi(THF)]2 and Zn[LPhLi(THF)]2, respectively, regardless of the stoichiometry of the starting materials. Alkane elimination reactions of ZnEt2 with one equiv. of H2LtBu or H2LPh in THF generate Zn2(LtBu)2(THF) or Zn2(LPh)2(THF)2, whereas those employing two equiv. of the protio ligands afford Zn(LtBuH)2(MeCN) or Zn(LPhH)2(MeCN), respectively. The X-ray structures of Zn[LtBuLi(THF)]2, Zn2(LtBu)2(THF), Zn2(LPh)2(THF)2, and Zn(LtBuH)2(MeCN) are presented.