Treatment of ZrCl 4 with LiC 6F 5, followed by addition of 1,4,7,10-tetraoxacyclododecane (12-crown-4) or N, N, N′, N′-tetramethylethylenediamine (tmed), leads to the isolation of two pentafluorophenylzirconate complexes: [Li(12-crown-4) 2] 2[ZrCl 2(C 6F 5) 4] ( 1) and [Li(tmed) 2][Li(tmed)] 2[ZrF 2(C 6F 5) 5] ( 2). The presence of Zr–F groups in the latter compound shows that C–F bond activation has occurred. The anion in the former complex adopts an octahedral structure owing to the π-donor character of the chloride ligands, whereas the anion in the latter adopts a regular pentagonal bipyramidal structure. The lithium atoms in 1 are not interacting with the anion, whereas two of the lithium atoms in 2 are involved in Li⋯F interactions with fluorine atoms in the anion. Selected bond distances and angles for 1: Zr–C=2.478(5)–2.510(5), Zr–Cl=2.409(5), 2.435(5) Å, C–Zr–C( cis)=77.9–106.9(2), C–Zr–C( trans)=161.1, 169.1(2), Cl–Zr–Cl=166.7(2)°. Selected bond distances and angles for 2: Zr–C=2.432–2.449(8), Zr–F=1.986(4), Li⋯F=1.73(2)–2.50(2) Å, C–Zr–C( cis)=69.6–73.3, F–Zr–F=178.8(2)°. Crystal data for 1: monoclinic, space group P2 1/ n, a=15.2288(14), b=17.328(2), c=24.013(2) Å, β=91.936(3)°, V=6333(1) Å 3, Z=4, wR 2=0.2985 for 7801 reflections and 722 parameters. Crystal data for 2: monoclinic, space group P2 1/ n, a=11.6143(5), b=29.6561(9), c=20.4427(8) Å, β=103.266(1)°, V=6853.3(4) Å 3, Z=4, wR 2=0.1822 for 8762 reflections and 759 parameters.