Nanoscale [(Ba 0.85 Ca 0.15) 0.995 Nd 0.005 ](Ti 0.9 Hf 0.1)O 3 (Nd-BCTH) ceramics were prepared via the hydrothermal method, and the effects of sintering temperature and holding time on the phase structure, micromorphology, electrical and optical properties of the Nd-BCTH ceramics were explored. All the Nd-BCTH ceramics present rather pure perovskite structure with composition approaching rhombohedral phase around the morphotropic phase boundary (MPB) region. The highest relative density is obtained for the sample sintered at 1220 °C for 10 h. The existence of Ba2+, Ca2+, Ti4+, Hf4+ and Nd3+ is confirmed and the elements distribute rather uniformly detected by X-ray photoelectron spectrometer (XPS) and energy dispersive X-ray (EDX) analysis. The ceramics present nanoscale grain size, which tends to increase with the increase of sintering temperature and holding time, and significantly affects dielectric constant and Curie temperature. Very thin and narrow ferroelectric hysteresis loops are observed, where a considerable energy storage density (173.88 mJ/cm3) and high energy storage efficiency (80.68%) are obtained at low electric field. The increase of sintering temperature and holding time induces a red shift at 400 nm absorption edge and a blue shift at 300 nm absorption edge in the Nd-BCTH ceramics, and all ceramics have a maximum absorption value at around 260 nm. Under the excitation of 269 nm light, the Nd-BCTH ceramics show the strongest fluorescence peak at 473 nm, corresponding to the 4G 3/2 →4I 9/2 transition, emitting indigo blue fluorescence. When the ambient temperature is above 400 °C, grains conduction dominates the conductive mechanism in the nano-sized Nd-BCTH ceramics. Such conduction can be attributed to oxygen vacancies caused due to the evaporation of alkaline-earth metals during high temperature sintering, and show typically thermally excited relaxation process. • Pure perovskite structure Nd-BCTH ceramics are prepared via the hydrothermal method. • The Nd-BCTH ceramics present a dense microstructure and all elements distribute evenly. • The dielectric constant and Curie temperature decrease, and piezoelectric properties lose due to the nanometer grain size. • The ceramics have very thin and long hysteresis loops, and present excellent low electric field energy storage performance. • Via Nd doping, the ceramics present strong fluorescent performance and realize multi-functionality. [ABSTRACT FROM AUTHOR]