We demonstrate 230 to 250 nm efficient ultraviolet (UV) photoluminescence (PL) from AlN(AlGaN)/AlGaN multi-quantum-wells (MQWs) fabricated by metal-organic vapor-phase-epitaxy (MOVPE). Firstly, we show the PL spectra of AlxGa1—xN on SiC over the whole compositional range, i.e. from GaN to AlN, emitting from near band-edge. We observed a drastic intensity enhancement of PL emission by small incorporation of GaN into AlN. We systematically investigated the PL properties of AlGaN MQWs consisting of wide bandgap AlGaN (Al content: 53 to 100%) barriers. We obtained efficient PL emission of 234 and 245 nm from AlN/Al0.18Ga0.82N and Al0.8Ga0.2N/Al0.18Ga0.82 MQWs, respectively, at 77 K. The emission from the AlGaN MQWs were several ten times stronger than that of bulk AlGaN. We found that the PL from AlGaN MQW is as efficient as that of InGaN QWs at 77 K.