We have investigated the effect of substrate temperatures ranging from 680 °C to 800 °C on the orientation of pulsed laser deposited YBa2Cu3O7−x.(YBCO) thin films on (100) LaAlO3 substrates. X-ray diffraction studies indicate that there is a progressive change in the dominant orientation of the films from c-axis oriented (c-axis perpendicular to the substrate surface) to a-axis oriented (a-axis perpendicular to the substrate surface) grown as the substrate temperature is lowered. Two YBCO bilayers, which are the a-axis oriented YBCO film on the top of c-axis oriented YBCO film (a/c) bilayer and c-axis oriented YBCO film on the top of a-axis oriented YBCO film (c/a) bilayer, have been grown by in situ two step pulsed laser deposition and were characterized by scanning electron microscopy (SEM), Rutherford backscattering (RBS) spectrum, x-ray diffraction (XRD), and Tc measurements. Through SEM and XRD studies, double layer structures of the a/c and c/a bilayers were confirmed indirectly.