Abstract We investigate the structural and electrical properties of AlxIn1–xN/AlN/GaN heterostructures with AlGaN buffers grown by MOCVD, which can be used as an alternative to AlInN HEMT structures with GaN buffer. The effects of the GaN channel thickness and the addition of a content graded AlGaN layer to the structural and electrical characteristics were studied through variable temperature Hall effect measurements, high resolution XRD, and AFM measurements. Enhancement in electron mobility was observed in two of the suggested AlxIn1−xN/AlN/GaN/Al0.04Ga0.96N heterostructures when compared to the standard AlxIn1–xN/AlN/GaN heterostructure. This improvement was attributed to better electron confinement in the channel due to electric field arising from piezoelectric polarization charge at the Al0.04Ga0.96N/GaN heterointerface and by the conduction band discontinuity formed at the same interface. If the growth conditions and design parameters of the AlxIn1−xN HEMT structures with AlGaN buffers can be modified further, the electron spillover from the GaN channel can be significantly limited and even higher electron mobilities, which result in lower two-dimensional sheet resistances, would be possible.