AlScN is attractive as a lattice-matched epitaxial barrier layer for incorporation in GaN high electron mobility transistors due to its large dielectric constant and polarization. The transport properties of polarization-induced two-dimensional (2D) electron gas of densities of ∼2×1013/cm2 formed at the AlScN–GaN interface is studied by Hall-effect measurements down to cryogenic temperatures. The 2D electron gas densities exhibit mobilities limited to ∼300 cm2/V s down to 10 K at AlScN/GaN heterojunctions. The insertion of a ∼2 nm AlN interlayer boosts the room temperature mobility by more than five times from ∼300 cm2/V s to ∼1573 cm2/V s, and the 10 K mobility by more than 20 times to ∼6980 cm2/V s at 10 K. These measurements provide guidelines to the limits of electron conductivities of these highly polar heterostructures.