The treatment of Schiff base HL [HL=3,5-(t-Bu)(2)-2-HOC6H2CH=N-8-C9H6N] with 1 equiv. n-BuLi in THF followed by reacting with 1 equiv. YbCl3 gives the ion-pairs ytterbium Schiff base complex YbLCl3Li(DME)(3) (1). The complex I was characterized by elemental analysis, IR spectra, and X-ray structural determination. The crystal data of complex I are monoclinic, P2(1)/n space group, a=1.4855(16) nm, b=1.3696(13) nm, c=2.1816(2) nm, alpha=90.00 degrees, beta=98.217(3)degrees, gamma=90.00 degrees, V=4.3748(8) nm(3), Z=4, F(000)=1868, M-r=916.17, D-c=1.397 g.cm(-3), mu=2.364 mm(-1), R-1=0.0855, wR(2)=0.1863.