Efficient multi-path heat dissipation is urged to be designed for balancing the heat density generated in highly integrated electronic devices. Herein, aluminum foam/carbon composites were fabricated by chemical bath and annealing method to realize the effect of strengthening the effective thermal conductivity while retaining the convective heat transfer characteristics of the porous structure. The results show that the continuous and high crystalline carbon coating can be obtained in the optimized composites prepared with 350 g dopamine addition at 600 °C annealing temperature. When compared with amorphous carbon, the phonons in crystalline carbon can carry more energy during the heat transport in terms of high phonons density of states, and their scattering behavior can be alleviated. A smaller temperature gradient is further established in the system. Hence, a desirable thermal conductivity, 21.44 W m K, is obtained in the optimized composites, which is almost 3 times that of pristine aluminum foam (7.67 W m K). Additionally, the remarkable cooling efficiency of 24.71% in comparison to other studies, suggests that aluminum foam/carbon composites hold great potential as thermal management materials in addressing the issue of intense heat generation.