A series of new azomethine dimers was synthesized by the condensation reaction of flexible bis-benzaldehydes with four aromatic amines containing phenyl, naphthyl, anthracene and pyrene groups. Their right structure was confirmed by FTIR and 1H-NMR spectroscopy and their thermal properties were investigated by thermogravimetric analysis, differential scanning calorimetry and polarized light optical microscopy. A view on their photophysical behavior was gained by UV-vis and photoluminescence spectroscopy. The dimers containing pyrene and anthracene presented liquid crystalline behavior, while the other dimers were crystalline compounds. Two dimers containing pyrene moieties formed mesomorphic glasses and had intense luminescence, promising properties for applications in building optoelectronic devices.