AbstractThree different compositions (9 : 1, 7 : 3, and 1 : 1) of poly(ethyl methacrylate) (PEMA) and poly(vinyl acetate) (PVAc) are chosen to check the miscibility of a polymer pair. The 9 : 1 and 7 : 3 PEMA‐PVAc blends are immiscible and have shown two distinct loss peaks in dynamic mechanical analysis (DMA) studies, while 1 : 1 PEMA‐PVAc has shown a single loss peak. Immiscible composition 7 : 3 PEMA‐PVAc is selected to study the effect of cholesteryl additives on the miscibility of the polymers. The additives chosen for the present studies are cholesteryl chloride, cholesteryl caprylate, and cholesteryl laurate. The DMA studies showed that all the additives caused a merging of the two loss peaks into one. X‐ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) studies of the blend and blend with additive samples are utilized to get further information. The FTIR studies do not show any detectable change. The SEM micrographs of the blend and cholesteryl additive systems show a single‐phase ordered structure, and XRD data studies indicate the presence of small crystallites.