In the present work, the new aluminium-substituted polyoxometalates of the Anderson-Evans type have been prepared and structurally defined by the reaction of aluminium (III) chloride hexahydrate and sodium tungstate dihydrate/sodium molybdate dihydrate in an aqueous basic medium. Elemental analysis, FT-IR, TGA, 1H NMR, and 31P NMR analysis revealed that these polyoxometalates had the following formula: [Ph4P]3[Al(OH)6Mo6O18]·4H2O 1, [Ph4P]3[Al(OH)6W6O18]·4H2O 2, [C7H10N]3[Al(OH)6Mo6O18]·4H2O 3, [C7H10N]3[Al(OH)6W6O18]·4H2O 4. The compounds 1 and 2 show promising antibacterial activity against gram-positive Staphylcoccus aureus ATCC 25923 and gram-negative Escherichia coli ATCC 25922 bacteria.