The in situ metalorganic chemical vapor deposition (MOCVD) growth of Al 2 O 3 dielectrics on β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 films is investigated as a function of crystal orientations and Al compositions of β-(Al x Ga 1−x ) 2 O 3 films. The interface and film qualities of Al 2 O 3 dielectrics are evaluated by high-resolution x-ray diffraction and scanning transmission electron microscopy imaging, which indicate the growth of high-quality amorphous Al 2 O 3 dielectrics with abrupt interfaces on (010), (100), and [Formula: see text] oriented β-(Al x Ga 1−x ) 2 O 3 films. The surface stoichiometries of Al 2 O 3 deposited on all orientations of β-(Al x Ga 1−x ) 2 O 3 are found to be well maintained with a bandgap energy of 6.91 eV as evaluated by high-resolution x-ray photoelectron spectroscopy, which is consistent with the atomic layer deposited (ALD) Al 2 O 3 dielectrics. The evolution of band offsets at both in situ MOCVD and ex situ ALD deposited Al 2 O 3 /β-(Al x Ga 1−x ) 2 O 3 is determined as a function of Al composition, indicating the influence of the deposition method, orientation, and Al composition of β-(Al x Ga 1−x ) 2 O 3 films on resulting band alignments. Type II band alignments are determined at the MOCVD grown Al 2 O 3 /β-(Al x Ga 1−x ) 2 O 3 interfaces for the (010) and (100) orientations, whereas type I band alignments with relatively low conduction band offsets are observed along the [Formula: see text] orientation. The results from this study on MOCVD growth and band offsets of amorphous Al 2 O 3 deposited on differently oriented β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 films will potentially contribute to the design and fabrication of future high-performance β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 based transistors using MOCVD in situ deposited Al 2 O 3 as a gate dielectric.