Quaternary InAlGaN alloys are attracting much attention as candidate materials for realizing deep ultraviolet (DUV) light‐emitting diodes (LEDs). In this study, we investigated the effect of Si‐doping in the quaternary InAlGaN quantum well (QW) emitting region for obtaining a high efficiency DUV emission. Quaternary InAlGaN multi (M)‐QWs with Si‐doped InAlGaN buffer and barrier layers were grown on sapphire (0001) / AlN / AlGaN template by low‐pressure metal‐organic chemical‐vapor deposition (LP‐MOCVD). We found that the surface roughness of InAlGaN layer was significantly improved by introducing the light‐doping of Si. The oxygen impurity concentration in the quaternary InAlGaN layer was significantly reduced by the small amount of Si‐doping. We also revealed that the emission efficiency of the InAlGaN QW was markedly improved by inserting thin (3‐nm‐thick) undoped InAlGaN interlayer between n‐AlGaN buffer and n‐InAlGaN layers. At last, we demonstrated extremely high intensity PL emission from 280 nm‐band InAlGaN QWs at room temperature (RT). The ratio of the integrated intensity of the RT‐PL against the 77 K‐PL was 86%. This result suggests that the internal quantum efficiency (IQE) of the InAlGaN‐QW is considerably high. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)