Accurately extracting capacitances among the interconnects in modern multi-dielectric technology of integrated circuits is a challenging task. The floating random walk (FRW) algorithm is advantageous for capacitance extraction and has been extended by W. Yu et al. to accurately handle multi-dielectric structures with a precharacterization approach. In this paper, we improve this pre-characterization approach by permitting the cubic transition domains with three or four-dielectric layers. The techniques of pre-characterizing and utilizing these multi-dielectric transition cubes are proposed. Experiments on the test cases under actual manufacture technologies show that the proposed method brings 13× speedup on average, with affordable memory overhead. The experiments also validate the accuracy of the proposed method and reveal the significant error caused by the dielectric homogenization approach in a commercial FRW solver. Finally, on a machine with 12-core CPU, the parallel FRW algorithm equipped with the proposed pre-characterization method demonstrates more than 10× speedup of parallelization.