A series of rigid hexadentate salen-type (H2L) ytterbium complexes, namely, [Yb2L3(CH3OH)]center dot 3CH(3)CN (1), [Yb2LL'L ''(CH3OH)(H2O)(2)](ClO4)(2)center dot CH3OH center dot H2O (2), [Yb2L(OAc)(4)(CH3OH)(2)]center dot 2CH(3)OH (3), and {[Yb2L(OAc)(4)]center dot 3H(2)O}(n) (4) (H2L = N,N'-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine, HL' = 2-(2'-hydroxy-3'-methyloxy-phenyl)benzimidazole and HL '' = 3-methoxysalicylaldehyde) have been synthesized by reactions of H2L with multifarious Yb3+ salts. X-ray crystallographic analyses demonstrate that complex 1 is of a triple-decker sandwich-type Yb2L3 structure with a ratio of H2L/Yb = 3:2, 2 and 3 possess the unique Yb-2 core with a ratio of H2L/Yb = 2:2 and 1:2, respectively, 4 exhibits one dimensional coordination polymers in which the polymeric structures are formed by acetate (OAc-) groups. All complexes 1-4 exhibit near-IR luminescence, which can be rationalized on the basis of the disparate structural effects. The magnetic analysis unveils that all complexes 1-4 are of field-induced single-molecule magnet behavior with the energy barriers (U-eff/k(B)) of 14.5, 2.0, 9.5, and 2.4 K at 3 kOe direct current fields, respectively.