This study for the first time discovered miscibility in the binary blend of semicrystalline poly(ethylene oxide) (PEO) with amorphous poly(benzyl methacrylate) (PBzMA). Differential scanning calorimetry, optical and scanning electron microscopy, and infrared spectroscopy were performed to characterize and demonstrate miscibility in the PEO/PBzMA system. The glass-transition behavior and Fourier transform infrared results suggest that the intermolecular interactions between the pairs were likely nonspecific and at best comparable to those among the same constituent component. The melting-point depression study yielded chi = -0.1, indicating a relatively low interaction strength. It is concluded that the phase behavior of the blend was miscibility with nonspecific interactions, mostly a matched polar-polar intermolecular attraction. PEO spherulitic crystallization in the blend is discussed to support the miscibility behavior.