Poly(methyl methacrylate)/poly(styrene-co-maleic anhydride) (PMMA/SMA) blends with various compositions were prepared through solution casting and melt blending. Two preparation routes, solution casting and melt blending, were used to achieve different degrees of molecular entanglement in the samples with solution casting giving rise to a lower degree of entanglement. Therefore, the effect of molecular entanglement on molecular dynamics and phase-separation kinetics of PMMA/SMA blends was investigated by using broadband dielectric spectroscopy and small-angle laser light scattering (SALLS). Molecular entanglement is found to have a pronounced effect on the alpha-relaxation process. The glass transition temperature (T-g) is related to the degree of entanglement and a higher degree of entanglement can result in a higher T-g which shifts to a higher temperature after annealing. The relaxation time (tau) of the alpha-relaxation process is lower for lower degrees of entanglement. Neither the dynamics nor the distribution width of the beta-relaxation process is affected by degree of entanglement, regardless of the blend composition. The kinetics of phase-separation by spinodal decomposition (SD) in PMMA/SMA blends are however significantly influenced by the degrees of entanglement with decomposition rate being higher at lower degrees of entanglement. (C) 2012 Elsevier Ltd. All rights reserved.