A new Cd(II) complex with the monodentate ligand 3-fluoroaniline, CdCl2(C6H4FNH2)(2), has been prepared and characterized by single crystal X-ray diffraction, solid state NMR, IR, Raman and UV-visible spectroscopies. In the complex, the Cd(II) ion is surrounded by four chlorine atoms and two nitrogen atoms, forming a chain of edge-charing octahedra spreading along the a-axis direction. These chains are interconnected via N-H center dot center dot center dot Cl hydrogen bonds to form inorganic layers parallel to the (a, b) plane. The organic 3-fluorophenyl groups are inserted between these layers and are interconnected via C-H center dot center dot center dot F hydrogen bonds to perform an infinite three-dimensional network. Intermolecular pi-pi stacking interactions between neighboring aromatic rings are also observed with a face-to-face distance of 3.6816 (4) angstrom. The C-13 and F-19 CP-MAS NMR spectra are in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the different atoms. The absorption bands of the Cd2Cl4N2 units were identified by Raman spectroscopy. The solid-state UV-vis spectrum of the complex has been assigned to ligand and charge transfer transitions.