Photoluminescence (PL) and photoreflectance (PR) were used to characterize ZnxCd1-xSe/MgSe multiple quantum well (MQW) structures grown on InP substrates by molecular beam epitaxy for mid-infrared (IR) device applications. The PL spectra yielded information of the fundamental excitonic recombination and ZnxCd1-xSe cap/spacer band edge emission of the samples. The PR spectra revealed multitude of possible interband transitions in MQW structures. The ground state transitions were assigned by comparing with the PL emission signals taken from the same structures. A comprehensive analysis of the PR spectra led to the identification of various interband transitions. The intersubband transitions were then estimated and found to be in a good agreement with the previous report of Fourier-transform IR absorption measurements [Li etal, Appl. Phys. Lett. 92, 261104 (2008)]. The results demonstrate the potential of using PL and PR as nondestructive optical techniques for characterization of ZnxCd1-xSe/MgSe MQWs for mid-IR device applications.