This paper is dedicated to electro-physical characterisation of a GaAs p-i-n structure grown for solar cell applications, which was carried out by light and dark current-voltage (I–V) and Deep Level Transient Fourier Spectroscopy (DLTFS) methods. The conversion efficiency and open-circuit voltage were determined from I–V measurement at 1 and 20× sun light concentrations. Three electron like defects TAn1, TAn2, TDn and one hole like defect TBp obtained by DLTFS measurements were confirmed. The origin of these defect states was stated as native GaAs impurities.