The important effect that even a small change in the nature of the side chain of a component of a blend has in its miscibility level was observed in a series of blends of phenoxy (Ph) with poly(methacrylates). Thus, while the Ph/poly(methyl methacrylate) blends are miscible and the Ph/poly(ethyl methacrylate) blends partially miscible, Ph/poly(butyl methacrylate) blends were almost fully immiscible. The observed miscibility of Ph/poly(butylmethyl methacrylate) indicates that the change in a component of a miscible blend of some pendant units that give rise to miscibility, by those from a different second component, which give rise to immiscibility is less important. The observed decrease in the strength of the beta secondary transition of Ph was clearly related to the miscibility level of the blends. The negative effects on properties of a very low molecular weight material can be overcame by blending with a miscible second component, rendering the overall molecular weight of the blend above the critical value. The change in the nature of the side chain, apart from the negative effect on fracture properties such as ductility, also had considerable effect on the short-term mechanical properties such as modulus of elasticity and yield stress.