Poly(methyl methacrylate) (PMMA) was introduced into ferroelectric Poly(vinylidene fluoride-co-trifluoroethylene) P(VDF-co-TrFE) via a simple solution blending process and a series of P(VDF-co-TrFE)/PMMA blends with varied PMMA content was obtained in an effort to investigate the confinement effect of PMMA on the crystalline, dielectric, and electric energy storage properties of P(VDF-co-TrFE). PMMA addition could reduce the crystallinity dramatically as well as the crystal size due to its dilution effect and impediment effect on the crystallization of P(VDF-co-TrFE). PMMA introduction is also responsible for the phase transition of P(VDF-co-TrFE) from α phase into γ phase. As expected, both the dielectric constant and loss of the blends are reduced as PMMA addition increases for the dilute, decoupling, and confinement effect of PMMA on the relaxation behavior of crystal phases of P(VDF-co-TrFE) under external electric field. As a result, both the maximum and remnant polarization of the blends are significantly depressed. The irreversible polarization of P(VDF-co-TrFE) is effectively restricted by the addition of PMMA due to its impeding effect on the crystallization of P(VDF-co-TrFE) and restricting effect on the switch of the polar crystal domains. Therefore, the energy loss induced by the ferroelectric relaxation of P(VDF-co-TrFE) is significantly reduced to less than 25% at an electric field of 450 MV/m while the energy storage density is well maintained at about 10 J/cm−3 in the blend with 30 wt % PMMA. The results may help to understand how the ferroelectric relaxation affects the energy loss of ferroelectrics fundamentally and design more desirable materials for high energy storage capacitors. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40114.