The reaction of bulky phenols with H₃Al·NMe₃ afforded the new primary phenoxyalanes Mes*OAlH₂·NMe₃, 2 (Mes* = 2,4,6-^tBu₃-C₆H₂-), 2,6-Dipp₂C₆H₃OAlH₂·NMe₃, 3 (Dipp = 2,6-ⁱPr₂C₆H₃-), and 2,6-Trip₂C₆H₃OAlH₂·NMe₃, 4 (Trip = 2,4,6-ⁱPr₃C₆H₂-) as colorless crystalline solids. Subsequent reactions of 2,6-^tBu₂-4-MeC₆H₂OAlH₂·NMe₃, 1, and 2 with oxygen sources such as (Me₂HSi)₂O or Me₂SO gave the disiloxyalane 2,6-^tBu₂-4-Me-C₆H₂OAl(OSiHMe₂)₂·NMe₃, 5, and the alumoxane (Mes*OAlO·OSMe₂)₄, 6. The latter compound is a rare example of a species featuring an unsupported eight-membered (Al-O)₄ ring. The new compounds were characterized by ¹H and ¹³C{¹H} NMR and IR spectroscopy and elemental analyses, and compounds 3 and 6 were also characterized by single crystal X-ray diffraction.