Magnetocaloric effect (MCE) and magnetic torque measurements have been carried out in the π–d system λ-(BETS)2FeCl4 [BETS = bis(ethylenedithio)tetraselenafulvalene], which shows an antiferromagnetic insulating (AFI) phase below ∼8.5 K. In the magnetic torque curve, a sharp structure at ∼1.2 T and a step at ∼10 T are observed at low temperatures, which are caused by the spin-flop (SF) transition and the transition from the AFI to paramagnetic metallic (PM) phase, respectively. The MCE, directly related to the magnetic entropy, shows a small sharp peak at the SF transition and a sharp dip at the AFI–PM transition. The overall feature above 3 K is qualitatively interpreted by a simple picture: antiferromagnetic (AF) π spins and paramagnetic 3d spins at the Fe sites. However, a broad dip in the MCE is additionally found at ∼5 T below ∼3 K, which is not explained by the above picture. The results are compared with those of κ-(BETS)2FeBr4, which shows an AF order of the 3d spins at the Fe sites.