Ionic liquid is increasingly being used as a chemical modulator of multi‐walled carbon nanotubes (MWCNT). Here, we report the practical method for producing biodegradable electromagnetic interference (EMI) shield films made of thermoplastic polyurethane (TPU), polybutylene adipate‐co‐terephthalate (PBAT), and 1‐(2‐aminoethyl)‐3‐methyl‐1H‐imidazol‐3‐ium modified MWCNT (MIL). The field emission scanning electron microscopy study of cryo‐fractured 50:50 PBAT/TPU blend giving co‐continuous morphology and subsequent polymer EMI shield nanocomposite material had shown the co‐continuous nanofiller distribution. The nanoparticles were chosen to be distributed in the PBAT portion, according to subsequent research employing HRTEM and DMA. The electrical percolation threshold (EPT) is determined to be situated within 1–3 wt% of nanoparticles loading as the remarkable shift in total EMI shielding efficiency from −14.6 dB (for 1 wt%) to −28.6 dB (for 3 wt%) of nanoparticle‐loaded film at 10 GHz (in X‐band region) for a 0.8 mm thick film reveals that the EPT is approximately at 2 wt% of nanoparticle loading. The effective EMI shielding of −37.3 dB was achieved by 10 wt% of MIL loading.