Single crystals of a Y(III)–Re(V)(salen) tetranuclear complex have been obtained by the reaction between the [ReO(salen)(OMe)] and Y(hfac) 3 ·2H 2 O compounds (where salen 2− is the N,N′ - ethan-1,2-diylbis(salicylidenamine) ligand and hfac − is the 1,1,1,5,5,5-hexafluoroacetylacetonate ligand). This crystallizes in the triclinic, space group P1¯ (No. 2). The lattice parameters are a=12.222(5)Å, b=12.783(5)Å, c=15.222(4) Å, α=86.276(5)°, β=82.220(5)°, γ=82.396(5)°, V=2332.9(15)Å 3 with Z=2. The crystallographic structure of the {[Re(salen)] 2 O 3 [Y(hfac) 3 (H 2 O)] 2 }(CHCl 3 ) 2 (CH 2 Cl 2 ) 2 tetranuclear complex is composed of two terminal Y(hfac) 3 (H 2 O) moieties bridged by the linear central {[ReO(salen)] 2 O} entity.