This paper reports on the influence of sintering additives CuO and MgO on the recently developed lead-free electrocaloric (EC) material Ba0.82Sr0.18Sn0.065Ti0.935O3 (BSSnT-18-6.5). Details on the sintering behavior and the resulting microstructure of bulk ceramic samples prepared through solid-state synthesis and their dielectric, ferroelectric, and electrocaloric properties are presented. On the one hand, the addition of CuO (xCuO = 2%) significantly reduced the sintering temperature from 1400 °C to 1150 °C. On the other hand, the addition of MgO (xMgO = 1%) dramatically reduced the average grain size from 40 µm to 0.4 µm, leading to an increase in dielectric breakdown strength from 4.4 V µm−1 to 7.7 V µm−1. Thus, BSSnT-18-6.5 with the addition of MgO to bulk ceramic samples could achieve maximum EC temperature changes (|ΔTEC|) of 0.27 K around 30 °C with almost no aberration within a broad temperature range from 5 °C to 50 °C under an applied electric field change of 5 V µm−1. The results show the potential of this material for the fabrication of multilayer ceramic (MLC) components for future electrocaloric applications.