Al(PF3)(2) is produced by reaction of ground-state Al atoms with PF3 in an adamantane matrix at 77 K in a rotating cryostat. This new Al(0) complex has the magnetic parameters a(Al)(1) = 87 MHz, a(p)(2)= 160 MHz a(F)(6) = MHz, and g = 2.0040, values that are consistent with a(2)B(1) ground-state in C-2v symmetry.