In this study, polyimide (PI)/MXene hybrid composite films as electromagnetic interference (EMI) shielding materials were fabricated using MXene (Ti3C2Tx) as a filler. The PI/MXene nanohybrid composite films were fabricated by casting an aqueous solution containing water-soluble poly (amic acid) ammonium salt (PAS) and MXene colloid, followed by thermal imidization. PI/MXene hybrid composite films with different contents (1.36 wt. % ∼ 20 wt. %) were prepared. The PI/MXene hybrid composite films showed high EMI shielding effectiveness up to 159 dB/mm as well as low moisture contents, controlled dielectric constants, improved thermal stability, and low coefficients of thermal expansion.