Abstract The adsorption of Na on sputter-cleaned Al(100) and Al(111) single-crystal surfaces has been investigated under ultrahigh vacuum conditions. Sodium was deposited with an apertured ion source permitting quantitative dosage determination. Low energy electron diffraction patterns show well-ordered coherent structures corresponding to 1 2 monolayer on both surfaces, and 1 3 monolayer on Al(111). A hexagonal pattern corresponding to 7 8 monolayer occurs at a nonconforming dosage on Al(100), indicating a reduction in effective sticking coefficient. This result is verified by Auger intensity measurements, which show saturation beginning at 1 2 monolayer on both surfaces. Changes in contact potential with exposure were inferred from shifts in the low-energy cutoff of secondary electrons. The initial dipole moment is in good agreement with that on transition metal substrates, while the saturation value of the contact potential corresponds closely to the difference between reported work functions for bulk Al and bulk Na. A true minimum in the work function was not observed. Present results are compared with results obtained from transition metal substrates. Essential differences are attributed to the more metallic character of the bonding in the Al:Na system.