Thermal interface material (TIM) has a great potential for efficient heat management and safety of electronic devices. However, achieving high performance polymer-based TIM is still challenging because of its intrinsic thermal conductivity and weak mechanical properties. In particular, electromagnetic interference shielding effect (EMI SE) of polymer-based composites has a great attraction according to electronic devices have become ubiquitous, playing integral roles in everyday life in our increasingly interconnected world. Herein, a porous carbon cloth (CC) for use as a continuous thermally and electrically conductive template is prepared via a freeze-casting method, after which mxene (MX) is chemically grafted onto the CC surface. Then, the as-prepared MX-CC is used along with alumina (AO) to fill a poly vinyl alcohol (PVA) matrix in order to fabricate a thermally conductive film with electromagnetic interference (EMI) shielding properties. The resultant composite demonstrates remarkable characteristics, including an excellent EMI shielding effect of 28 dB, substantial tensile strength of 19 MPa, and impressive out of plane thermal conductivity (3.98 W/mK). When applied to a light-emitting diode (LED), the PVA/MX-CC/AO composite effectively manages heat, thereby resulting in a 49 °C reduction in the operating temperature. Therefore, the composites developed herein hold great promise for improving thermal management in electronic devices.