As one of the few Type I band offset, antimony-based material systems available for 3.3 to 4.2 micron mid-infrared multiple quantum well lasers, AlInAsSb alloys have been used as barriers with InAsSb wells. Previously, AlxIn(1-x)AsySb(1-y) quaternary alloys have been grown by MBE as random alloys up to an aluminum fraction, x = 0.10 on GaSb substrates and x = 0.15 on InAs substrates. Random alloy growth of quaternary films with increased aluminum content, although beneficial to the devices, is limited by a miscibility gap. We have used a digital alloy technique to grow stable, single phase, GaSb lattice-matched, optically smooth quaternary alloys for aluminum fractions of 0.05 to 0.5, well into the miscibility gap. DCXRD results show FWHM of 0th order alloy peaks are within 1.5 to 2 times that of the highly crystalline GaSb substrates and have well defined thickness fringes corresponding to the total film thickness and the digital alloy period. TEM images show very well ordered alloys with characteristic ultrathin superlattice structure having smooth interfaces, very little strain and atomic ordering limited to that imposed by the digital alloy technique. Photoluminescence measurements are used to fit a model for bandgap prediction from known alloy compositions. Theoretical studies have predicted that the addition of a fifth element, gallium, may help suppress Auger recombination through its effects on the subband structure. So, gallium is added to the quaternary to produce a quinternary alloy lattice-matched to GaSb. These AlGaInAsSb alloys have DCXRD and TEM results similar to the quaternary. The stable, single-phase growth of these quinternary alloys across the composition range is promising for improving the operating characteristics of mid-IR lasers.