We report the study of interband optical transitions in the interdiffused InAs quantum dash (QD) in InAlGaAs quantum well (QW) structures using room temperature surface photovoltage (SPV) spectroscopy. SPV signals have been detected from all relevant portions of both the as-grown and interdiffused structures including the QD, QW, and cladding layer. The effect of group-III intermixing on the interband optical transition energies in the interdiffused structures has also been revealed by the SPV spectroscopy, and the results have been confirmed by photoluminescence measurements. The SPV investigation shows that the compositional intermixing occurs not only between the dash and the surrounding well but also between the well and the surrounding barrier. The results demonstrate the potential of the SPV spectroscopy as a nondestructive, contactless method to characterize optical transitions in complex semiconductor nanostructures at room temperature.