Lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) ceramic exhibits excellent dielectric, ferroelectric and piezoelectric properties at the morphotropic phase boundary (MPB). Previously, we demonstrated that the use of the anionic surfactant sodium dodecyl sulfate (SDS, NaC12H25SO4) could enhance the dielectric properties of BCZT ceramic using surfactant-assisted solvothermal processing [1]. In the present study, structural, dielectric, ferroelectric properties, as well as electrocaloric effect and energy storage performances of this BCZT ceramic were thoroughly investigated. X-ray diffraction (XRD) measurements revealed the presence of single perovskite phase at room temperature with the coexistence of orthorhombic and tetragonal symmetries. In-situ Raman spectroscopy results confirmed the existence of all phase transitions from rhombohedral through orthorhombic and tetragonal to cubic symmetries when the temperature varies as reported in undoped-BaTiO3. Evolution of energy storage performances with temperature have been investigated. BCZT ceramic exhibits a high energy storage efficiency of ~ 80% at 120 °C. In addition, the electrocaloric responsivity was found to be 0.164 × 10−6 K·m/V at 363 K.