Luminescent piezoelectric materials promise a stratagem for controlling the optical process by electric field, which would benefit for future optoelectronic devices. Here, Er3+ doped (Ba0.85Ca0.15) (Zr0.1Ti0.9)O3 (BCZT: Er3+) piezoelectric ceramics are prepared to demonstrate the proof of concept. In addition to excellent intrinsic piezoelectricity and ferroelectricity, BCZT: Er3+ ceramics exhibit simultaneously strong green upconversion emissions under excitation of 980 nm. Remarkable photoluminescence (PL) quenching phenomenon as well as significant changes on relative intensities of stark lines are observed under external poling electric field. Furthermore, field dependent piezoelectric constant d33 and photoluminescence quenching ratio show similar variation trend and finally saturate for E > 3.5 kV/mm, which provides a noncontact strategy to monitor the piezoelectric constant d33. The PL quenching triggered by electric field in BCZT: Er3+ ceramics is ascribed to the decreased asymmetry originating from field-induced structural transformation from a significant fraction of the tetragonal phase to rhombohedral phase. Our work would be helpful for expanding the scope of luminescent piezoelectric materials and promising future optoelectronic and optical devices with cross-coupled physical properties.