This paper is the first of a series with the common theme of comparing thermal and acoustic pulse methods of measuring charge or polarization profiles across the thickness of slab‐shaped samples that are representative of different types of materials. In this paper, thermal and pressure pulse measurements are reported of the polarization distribution in poled, ferroelectric ceramic samples. The results obtained from both methods are complementary so that there is a benefit to using both. The results also demonstrate that large deviations from uniform polarization can be induced by processing differences.