In this work, we study the electronic properties of defects in the LaAlO3/SrTiO3 heterostructure, which is known to host a high mobility two-dimensional electron gas (2DEG) at the interface. This 2DEG also shows photoconductance, which could be related to defects that act as deep center trapping and releasing carriers by interaction with light. This phenomenon has raised an interest for the identification of deep energy levels in the LaAlO3/SrTiO3 heterostructure. We have studied the defect state properties using electrical characterization such as capacitance–voltage (C–V), current–voltage (I–V) measurements, and deep-level transient Fourier spectroscopy (DLTFS). From C–V and I–V analyses, a hysteresis was observed indicating an effect of mobile charges in the LaAlO3. Using DLTFS, we identify three defect states located at around 0.17 eV below conduction band and at 0.23 and 0.26 eV above the valence band. These defect states were attributed to defects in SrTiO3 such as strontium vacancies or titanium vacancies. We identify a fourth defect state having an energy of about 0.69 eV below the conduction band that could be related to oxygen vacancies in LaAlO3 or in SrTiO3. In addition, the observation of an effect of the electric field with DLTFS indicated that oxygen vacancies might be involved in Fowler–Nordheim or trap-assisted tunneling through the LaAlO3 layer.