Enhanced electrical resistivity about over two orders of magnitude for Na 0.5 Bi 2.5 Nb 2 O 9 (NBNO) high-temperature piezoceramics potentially used in piezoelectric sensors is achieved by the introduction of highly insulating Al 2 O 3 addition. Possible pyrochlore secondary phases of two types of grains: irregular polyhedral and platelike, forming at the grain boundaries, have significant blocking effect on the electric current paths and thus lead to improved electrical resistivity. Al 2 O 3 -modified NBNO ceramics show higher d 33 values up to 16.5 pC/N than that of pure NBNO ceramics (12.4 pC/N) because higher electric field is applied during poling process owing to enhanced electrical resistivity, whereas the T c values keep almost constant. A compromise between high T c , good polarizability and enhanced electrical resistivity has been achieved by suitable addition of Al 2 O 3 , which would shed light on how to obtain novel Aurivillius phase ferroelectrics for practical applications at high temperature.