In this letter, we report the pulsed atomic-layer epitaxy of ultrahigh-quality AlN epilayers and AlN/Al0.85Ga0.15N multiple quantum wells (MQWs) on basal plane sapphire substrates. Symmetric and asymmetric x-ray diffraction (XRD) measurements and room-temperature (RT) photoluminescence (PL) were used to establish the ultrahigh structural and optical quality. Strong band-edge RT PL at 208 and 228 nm was obtained from the AlN epilayers and the AlN/Al0.85Ga0.15N MQWs. These data clearly establish their suitability for sub-250-nm deep UV emitters.