The present invention provides an anisotropic, thermal conductive, electromagnetic interference (EMI) shielding composite including a plurality of aligned polymer nanofibers to form a polymer mat or scaffold having a first and second planes of orientation of the polymer nanofibers. The first plane of orientation of the polymer nanofibers has a thermal conductivity substantially the same as or similar to that of the second plane, and the thermal conductivity of the first or second plane of orientation of the polymer nanofibers is at least 2-fold of that of a third plane of orientation of the polymer nanofibers which is about 90 degrees out of the first and second planes of orientation of the polymer nanofibers, respectively, while the electrical resistance of each of the first and second planes is at least 3 orders lower than that of the third plane. A method for preparing the present composite is also provided.