Realization of heterostructures containing multiple two-dimensional electron liquids requires a fine control of the fabrication process. Here, we report a structural and spectroscopy study of LaAlO3/SrTiO3/LaAlO3 trilayers grown on the SrTiO3 substrate by pulsed-laser deposition. Scanning transmission electron microscopy with the help of ab initio calculations reveals that antisite defects associated with oxygen vacancies are primarily present in the SrTiO3 film (STO-f) close to the p-type interface (STO-f/LaAlO3), while oxygen vacancies prevail close to the top n-type interface (LaAlO3/STO-f). At the same interface, misfit dislocations relax the tensile strain of the top LaAlO3 layer. Combining x-ray absorption spectroscopy, x-ray linear dichroism, resonant photoemission spectroscopy, and electron energy loss spectroscopy, we observe that the 3d orbital reconstruction at the interface between LaAlO3 and the SrTiO3 substrate is confined over a few interfacial Ti planes while, at the top n-type interface (LaAlO3/STO-f), the absence of a dichroic signal can be related to the blurring of the interfacial orbital reconstruction due to the heterogeneity of defects.