A perylene-acetonitrile solution with TBAP (tetra-n-butylammonium perchlorate) electrocrystallizes on the electrode surface, under opportune conditions. It forms particular needle-like microcrystals that have been studied recently for their peculiar electrical and optical properties and for the fundamental processes involved in the electron transfer responsible for the electrocrystallization. These intriguing structures present various fractal-like morphological organizations and diverse crystal shapes on the same deposition process. Up to now these formations have been studied optically by conventional standard microscopy. We introduce here a novel methodology to collect information on the actual orientation and crystal structure by a near field optical setup with originally fabricated probes. We performed, for the first time on these samples, near field fluorescence imaging showing evidence that the perylene aggregations actually have a distinct optical orientation.