Organic single crystals are of particular fundamental interest as tools in probing the intrinsic electrical properties and the upper limit of performance for a given organic semiconducting molecule devoid of disorder. Rubrene single crystals are of particular interest in the field of organic electronics due to the high levels of charge carrier mobilities measured in transistors constructed of the same. In this thesis, we explore the properties of rubrene single crystal transistors. The photocurrent properties of rubrene single crystals are measured in ‘air-gap' transistors whose unique structure allows the measurement of photocarrier dynamics without the influence of a dielectric that can act as a source for traps. This structure has allowed us to identify phenomenon like persistent photoconductivity associated with the creation of oxygen related traps on the rubrene surface. Transient studies of the photocurrent reveal the presence of bimolecular recombination of the charge carriers. In addition, we have also performed optical spectroscopy studies including Raman spectra measurements which revealed the presence of endoperoxide related signature on the surface of the crystal while also confirming the low levels of intermolecular coupling present between the molecules. We have also explored the extrinsic factors that determine the surface conductivity of the rubrene crystal, particularly the presence of oxide related compounds on the surface of the crystal using XPS and photoluminescence measurements. The impact of photo-oxidation of the rubrene crystal on the surface conductivities were evaluated by a novel experiment involving the gradual photo-oxidation of the rubrene surface using a focussed laser. The creation of a deep acceptor state that can trap electrons indicates that the electrical properties of the rubrene surface like high unipolar p-type II conductivity and photoconductivity may be modulated by the presence of these oxygen induced states.