Lead-free piezoceramics are gaining importance for replacing widely used toxic lead-based PZT family. Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) is one such potential candidate that has attracted attention in recent years. Despite its high piezoelectric properties, BCZT suffers from a major drawback of low Curie temperature (Tc) that restricts its practical applicability. Numerous methods have been attempted to further improve its properties so as to make it a truly lead-free choice. In the present work, a systematic study is performed on BCZT ceramics synthesized from nanopowders produced by high-energy ball milling. It is found that there exists an optimum particle size of the starting powders at which piezoelectric charge coefficient (d33) of the corresponding ceramic is enhanced by 110% with a simultaneous increase in Tc by 7 °C. The study reveals that economically viable high-energy ball milling technique can be used to strengthen the candidature of BCZT ceramic system for replacing lead-based piezoceramics.