Four anion-dependent 0D Zn-II-Yb-III heterometallic Schiff base complexes, [YbZn2L2(OAc)(4)]center dot ClO4 (2), YbZnL2(NO3)(3) (3), [(YbL)(2)(H2O)-Cl(OAc)](2)center dot[ZnCl4](2) (4), and YbZnL(OAc)(4) (5), were assembled through central metal substitution or reconstruction from homotrinuclear Zn-II complex {[(Zn(OAc)(H2O)L](2)Zn}(ClO4)(2)center dot 4H(2)O [1; HL = 2-ethoxy-6-[(pyridin-2-ylmethylimino)methyl]phenol] with different (YbX3)-X-III salts [X = ClO4 (2), NO3 (3), Cl (4), and OAc (5)], in which the Zn-II-sensitized near-infrared luminescent performances in the four complexes 2-5 are closely related to their structural models.