We report the preparation of grain-aligned [Ca2CoO3−δ]0.62CoO2 (Ca349) thick films and the conversion of the easy axis of magnetization from the a-axis to the c-axis. The thick films were fabricated by a simultaneous usage of electrophoretic deposition and magnetic alignment methods (MEPD) at high deposition rate with the order of 10 mm/min. Moreover, a multi-layered thick film of Al2O3/Ca349/Al2O3/Ca0.9La0.1MnO3/Al2O3 was also fabricated by the MEPD method by the optimization of condition of each suspension. The conversion of the easy axis was performed crystallochemically for a [Bi2Sr2O4]0.55CoO2 (BiSr222) compound with the easy axis parallel to the a-axis in order to fabricate c-axis grain-oriented bulks by the magnetic alignment method. The substitution of Ca for Sr in the [(Bi0.5Pb0.5)2Sr2O4] block layer induced the change of the easy axis into the c-axis direction, and the magnetic anisotropy was increased by the partial substitution of rare earth elements of Pr, Nd, Tb and Dy for Ca. Using a compound of [(Bi0.5Pb0.5)2(Ca0.8Pr0.2)2O4]0.55CoO2, we have successfully prepared the c-axis grain-aligned bulk by the magneto-scientific method. Our present results indicate that the magneto-scientific method is one of the useful and realistic processes for production of thermoelectric modules.