For the first time, room-temperature electrocaloric (EC) and magnetocaloric (MC) effects were observed in multicaloric composites using direct characterization methods. By combining the EC ceramic 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 (PMN–10PT) with the MC La-Fe-Si-Co (LFSC) alloy, the multicaloric films were prepared. The PMN–10PT films exhibited a dielectric permittivity of ∼600, while composites exhibited improved values at ∼700. The room-temperature EC response of composites was ∼0.45 K at 250 kV cm−1, a 32% enhancement when compared to PMN–10PT films. This enhancement in composite films is attributed to Maxwell-Wagner-type polarization effects, induced by the embedded LFSC MC particles. The room-temperature MC response of composite films was directly characterized, achieving a MC response ∼1.4 K at 2 T, after corrections. Our results bring novel insights on the feasibility of preparing multicaloric composites with enhanced caloric properties for room-temperature micro-cooling technologies.