In the past 50 years, the electronic and communication industries have grown exponentially, which has caused major concerns about electromagnetic (EM) pollution. In recent years, more thrust has been given to development of polymer composites to lessen electromagnetic interference (EMI) pollution. In the present work, porous polydimethylsiloxane (PDMS) composite foams based on cobalt ferrite (CoFe 2 O 4 ) and reduced graphene oxide (rGO) are produced through the ammonium bicarbonate template approach. The resulting foams possess increased EMI shielding effectiveness via the absorption‐dominated mechanism due to the fact that PDMS foam functions as a three‐dimensional (3D) network, rGO offers the requisite conductive channel, and CoFe 2 O 4 produces the necessary magnetic loss. The total EMI shielding effectiveness (SE) of PDMS/rGO composite foams without CoFe 2 O 4 is 24 dB, however, with different weight percentages of CoFe 2 O 4 added (3%, 6%, and 9%), the EMI SE increases to 41 dB for 3 mm thickness. The heat insulation performance of the material is also studied, and the measured thermal conductivity is 0.0391 Wm −1 K −1 , which is very low value. The attributes of the composite foam underscore its excellent thermal insulation performance and its capacity for EMI shielding, rendering it highly suitable for diverse applications across various fields.