We present the characterization of new binary mixtures made of two rod-like molecules: a photosensitive azobenzene derivative (called J7) and a smectogen (called M11). The interest in these two specific compounds is related to their use as basic constituents of photo-active liquid crystalline elastomers and their opto-mechanic applications. Differential scanning calorimetry and polarized optical microscopy were used to characterize the phase diagram of the binary system J7-M11. H-2 NMR spectroscopy of the H-2-selectively labelled M11, either alone or as a probe in binary mixtures containing different ratios J7/M11, was applied to study the orientational ordering properties.