A series of InAlN/AlGaN five quantum well (QW) heterostructures was prepared by metal-organic vapour phase epitaxy to investigate their photoluminescence (PL) properties as a function of indium content in QWs at aluminium content in barriers fixed at 59%. In addition to the expected redshift of the emission spectrum, a strong rise of PL efficiency was observed with increasing indium content from 12.5 to 18%. Use of a higher indium content leads to a further redshift but also to a sudden and sharp degradation of PL efficiency. Reasons for the observed behaviour are discussed in detail, which raise the possibility of a transition to a type II band lineup in the InAlN-AlGaN system.