Luminescent materials with dynamic photoluminescence activity have aroused special interest because of their potential widespread applications. One proposed approach of directly and reversibly modulating the photoluminescence emissions is by means of introducing an external electric field in an in-situ and real-time way, which has only been focused on thin films. In this work, we demonstrate that real-time electric field-induced photoluminescence modulation can be realized in a bulk Ba0.85Ca0.15Ti0.90Zr0.10O3 ferroelectric ceramic doped with 0.2 mol% Pr3+, owing to its remarkable polarization reversal and phase evolution near the morphotropic phase boundary. Along with in-situ X-ray diffraction analysis, our results reveal that an applied electric field induces not only typical polarization switching and minor crystal deformation, but also tetragonal-to-rhombohedral phase transformation of the ceramic. The electric field-induced phase transformation is irreversible and engenders dominant effect on photoluminescence emissions as a result of an increase in structural symmetry. After it is completed in a few cycles of electric field, the photoluminescence emissions become governed mainly by the polarization switching, and thus vary reversibly with the modulating electric field. Our results open a promising avenue towards the realization of bulk ceramic-based tunable photoluminescence activity with high repeatability, flexible controllability, and environmental-friendly chemical process.