Vertically aligned carbon nanotube (VACNT) films with high thermal conductance and mechanical compliance offer an attractive combination of properties for thermal interface applications. In current work, VACNT films synthesized by the chemical vapor deposition method were used as thermal interface material (TIM) and investigated experimentally. The liquid metal alloy (LMA) with melting point of 59 °C was used as bonding material to attach VACNT films onto copper plates. In order to enhance the contact area of LMA with the contact surface, the wettability of the contact surface was modified by plasma treatment. The thermal diffusivity, thermal conductivity, and thermal resistance of the synthesized samples were measured and calculated by the laser flash analysis (LFA) method. Results showed that: (1) VACNT films can be used as TIM to enhance the heat transfer performance of the contact surface; (2) the LMA can be used as bonding material, and its performance is dependent on the LMA wettability on the contact surface. (3) When applying VACNT film as the TIM, LMA is used as the bonding material. After plasma treatment, comparison of VACNT films with the dry contact between copper and silicon showed that thermal diffusivity can be increased by about 160%, the thermal conductivity can be increased by about 100%, and the thermal resistance can be decreased by about 31%. This study shows the advantages of using VACNT films as TIMs in microelectronic packaging.