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The electrocaloric effect in the blends of poly(vinylidene fluoride–trifluoroethylene–chlorofluoroethylene) (P(VDF-TrFE-CFE)) with small amount of poly(vinylidene fluoride–trifluoroethylene) (P(VDF-TrFE)) is investigated. It was found that small amount of P(VDF-TrFE) (∼10 wt. %) can cause a more than 10% increase in the crystallinity in the blends. Although the two polymers form separate crystalline phases, the interfacial couplings to the random defects in the terpolymer convert the normal ferroelectric P(VDF-TrFE) into a relaxor ferroelectric. As a result, the blends with 10 wt. % of P(VDF-TrFE) exhibit a 30% increase in the adiabatic temperature change over the entire experimental temperature range (20 °C–60 °C).