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Ferroelectric perovskite materials are crucial candidates for the solid-state cooling devices due to their distinguished electrocaloric effect (ECE). Here we report the coexistence of negative and positive ECE in sol–gel derived single-layer (SL) Pb(ZrxTi1–xO3 (PZT) thin films with a composition close to the morphotropic phase boundary (MPB). A negative ECE of Δ T = − 1.81 K at 135 °C and positive ECE of Δ T = 0.64 K at 40 °C under an applied electric field of 374 kV cm−1 are achieved. Such appearance of negative and positive ECE at different temperatures is attributed to the transition from rhombohedral to tetragonal phase and associated with the effect of defect dipoles in SL-PZT thin films at MPB. [ABSTRACT FROM AUTHOR]