LPE growth of Ga1-xAlxAsySb1-y on (100) GaSb substrates has been investigated for wide range of aluminium content in the melt, x(Al)(1) = 0.01 - 0.06, various growth temperature, and various amount of supersaturation. Epilayers were characterised by means of XRD, TEM, EPXMA, and SIMS. It has been found that LPE growth at T approximate to 530 degreesC produces good quality Ga1-xAlxAsySb1-y layers with Al content in the solid up to x = 0.24 and lattice mismatch Deltaa/a not exceeding 5 . 10(-4). As for the growth of higher aluminium content alloys, at higher temperatures T = 590 - 600 degreesC, good results have been obtained unless the Al content in the melt does not exceed x(Al)(1) = 0.02 giving perfectly matched Ga1-xAlxAsySb1-y epilayers with Al content in the solid up to x = 0.3. By introducing an interlayer, either of lattice matched Ga0.91In0.09As0.08Sb0.92 or Ga0.70Al0.03As0.03Sb0.97, LPE growth from the melt with Al content up to x(Al)(1) = 0.06 becomes possible and enables fabrication of Ga1-xAlxAsySb1-y layers with Al content in the solid as high as x = 0.62. Ga1-xAlxAsySb1-y layers obtained from the melt with x(Al)(1) = 0.04 were characterised by lattice mismatch Deltaa/a = (8 - 9). 10(-4), an increase of Deltaa/a to 22 . 10(-3) was observed fix epilayers obtained from the melt with x(Al)(1) = 0.06.