The electrocaloric (EC) effect and energy storage properties of eco-friendly ferroelectric Ba0.9Sr0.1Ti1−xSnxO3 (BSTS-x) ceramics prepared by the conventional solid-state reaction method were studied. Significant energy efficiency exceeding 80% was found in our samples. In particular, BSTS-5 and BSTS-10 samples exhibit 92% and 88% efficiency, respectively, over a wide temperature range around room temperature (RT). Direct EC measurement and an indirect method based on the thermodynamic approach were used to characterize the EC effect, and both yielded consistent results. The largest electrocaloric responsivity of 0.73 K mm/kV was obtained for BSTS-0 at 368 K with an adiabatic temperature change ΔTEC of 0.55 K at a low applied electric field of only 7.4 kV/cm. With increasing Sn-content, the EC response of BSTS-x ceramics decreases, while their diffuseness increases over an extensive temperature range, centered at RT. A significant coefficient of performance (COP > 26) was found for our samples. The obtained results demonstrate the possibility of designing eco-friendly materials with higher EC effect and energy efficiency for potential solid-state refrigeration and energy storage devices.