We report on n-type degenerate doping in β-(Al0.26Ga0.74)2O3 epitaxial thin films grown by metalorganic vapor-phase epitaxy and modulation doping in β-(Al0.26Ga0.74)2O3/β-Ga2O3 heterostructures. Alloy composition is confirmed using high-resolution X-ray diffraction measurements. Carrier concentration in the thin films is proportional to the silane molar flow. Room-temperature Hall measurements showed a high carrier concentration of 6 × 1018 cm-3 to 7.3 × 1019 cm−3 with a corresponding electron mobility between 53-27 cm2 V-1 s-1 in uniformly doped β-(Al0.26Ga0.74)2O3 layers. Modulation doping is used to realize a total electron sheet charge of 2.3 × 1012 cm−2 in a β-(Al0.26Ga0.74)2O3/β-Ga2O3 heterostructure using a uniformly doped β-(Al0.26Ga0.74)2O3 barrier layer and a thin spacer layer.