A new 2D zinc(II) supramolecular complex [Zn(2,4-D)(o-phen)(H2O)(2)](NO3) (1) (2,4-D = 2,4-dichlorophenoxyacetic acid, o-phen = 1,10-phenanthroline), was synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, TG analysis, IR, and luminescence spectroscopy. For complex 1, each Zn-II ion lies in a pentacoordinate distorted quadrilateral pyramidal configuration. The 8-member-ring hydrogen bonds clusters result in 1D ladder-like supramolecular chains, which further stack up by face-to-face pi-pi stacking interactions into 2D supramolecular layers. The TG analysis shows that complex 1 has high thermal stability. The solution and solid-state photoluminescence of 1 are reported.