Staggered AlGaN quantum wells (QWs) are designed to enhance the transverse-electric (TE) polarized optical emission in deep ultraviolet (DUV) light- emitting diodes (LED). The optical polarization properties of the conventional and staggered AlGaN QWs are investigated by a theoretical model based on the k·p method as well as polarized photoluminescence (PL) measurements. Based on an analysis of the valence subbands and momentum matrix elements, it is found that AlGaN QWs with step-function-like Al content in QWs offers much stronger TE polarized emission in comparison to that from conventional AlGaN QWs. Experimental results show that the degree of the PL polarization at room temperature can be enhanced from 20.8% of conventional AlGaN QWs to 40.2% of staggered AlGaN QWs grown by MOCVD, which is in good agreement with the theoretical simulation. It suggests that polarization band engineering via staggered AlGaN QWs can be well applied in high efficiency AlGaN-based DUV LEDs.