Single crystal X-ray diffraction shows that [La(gly) 2 (H 2 O) 2 (phen) 2 (CH 3 CH 2 OH)](ClO 4 ) 3 (phen) 3 .3H 2 O (1), [Ln(gly) 2 (H 2 O) 2 (phen) 2 ](ClO 4 ) 3 (phen) 4 .nH 2 O [n=0, Ln=Nd (2); n=1, Ln=Ho (3)], and [Yb(gly) 4 (H 2 O)(phen)](ClO 4 ) 4 (phen) 2 (gly+H).2H 2 O (4) (gly=glycine, phen=1,10-phenanthroline) with the coordination number 9 for La 3 + , 8 for Nd 3 + and Ho 3 + , and 7 for Yb 3 + , exhibit the effect of lanthanide contraction. Complexes 1-4 are all mononuclear structures, with the ligand glycine coordinated to the Ln 3 + ion in the monodentate mode and in zwitterionic form. There exist free phen molecules and solvent molecules in the lattice. Therefore, there are different types of hydrogen bonding and π-π stacking interactions in the crystals that give rise to different supramolecular architectures. The structure of 1 is composed of 1D chains which extend in the [100] direction, while those of 2 and 3 are 2D structures extending in the (001) plane. However, complex 4 shows a complicated 3D network.