Exciton localization has been investigated via photoluminescence (PL) measurements for a 50 nm InGaAs/InAlAs wide quantum well (QW) lattice-matched to an InP substrate. Discrete QW emission bands from both localized exciton (LE) recombination and free exciton (FE) recombination were observed, demonstrating modified state filling with increasing pump power. An “S” shaped dependence of the FE peak energy on the temperature represents a signature of exciton activation and transition from LEs into FEs. The exciton localization energy was measured to be 8.87 meV in the QW, which is much larger than the values of ∼3.39 meV found in the reference InGaAs bulk. In addition, a slightly longer lifetime was measured for LE emission than that of FEs. These results provide an in-depth assessment of carrier localization in the InGaAs/InAlAs/InP heterostructures and provide useful information for the design of optical devices.