Two series of cyclometalated palladium(II) complexes based on Schiff bases and N-benzoylthiourea (BTU) ligands having four alkoxy groups at their periphery, with different number of carbon atoms, have been designed and prepared. The liquid crystalline behavior of these palladium(II) complexes was investigated by a combination of polarized optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction while their thermal stability was studied by thermogravimetric analysis (TGA). The palladium(II) complexes are thermally stable on a broad temperature range up to 230°C showing, depending on the alkoxy chain length, either monotropic or, for longest alkyl chain, enantiotropic smectic A and C phases. The luminescent properties of palladium(II) complexes were reported. These complexes show a yellow-orange solid-state emission at room temperature with two emission maxima at λmax around 580 and 650nm, respectively, with a shoulder around 710nm, when the samples are irradiated in the 330–380nm range.