The problem of achieving high light extraction efficiency in Al-rich Al x Ga −x 1 N is of paramount importance for the realization of AlGaN-based deep ultraviolet (DUV) optoelectronic devices. To solve this problem, we investigate the microscopic mechanism of valence band inversion and light polarization, a crucial factor for enhancing light extraction efficiency, in Al-rich Al x Ga −x 1 N alloy using the Heyd-Scuseria-Ernzerhof hybrid functional, local-density approximation with 1/2 occupation, and the Perdew-Burke-Ernzerhof functional, in which the spin-orbit coupling effect is included. We find that the microscopic Ga-atom distribution can effectively modulate the valence band structure of Al-rich Al x Ga −x 1 N. Moreover, we prove that the valence band arrangement in the decreasing order of heavy hole, light hole, and crystal-field split-off hole can be realized by using nanoscale (AlN) m /(GaN) n (m>n) superlattice (SL) substituting for Al-rich Al x Ga −x 1 N disorder alloy as the active layer of optoelectronic devices due to the ultra-thin GaN layer modulation. The valence band maximum, i.e., the heavy hole band, has p x -and p y -like characteristics and is highly localized in the SL structure, which leads to the desired transverse electric (TE) polarized (E⊥c) light emission with improved light extraction efficiency in the DUV spectral region. Some important band-structure parameters and electron/hole effective masses are also given. The physical origin for the valence band inversion and TE polarization in (AlN) m /(GaN) n SL is analyzed in depth.