Lead-free positive temperature coefficient of resistance (PTC) thermistors were synthesized from (1 À x/100)BaTiO 3 -(x/100)(Bi 1/2 K 1/2 )TiO 3 -based solid solutions, using a conventional mixed-oxide fabrication route, and sintered in N 2 followed by air annealing. A maximum T C of 205°C was achieved for x 5 20. An increase in x from 0 to 20 decreased the grain size by more than 92% and increased room temperature resistivity (q RT ) by 7 orders of magnitude. For x # 10, PTC ratio (q max /q min ) % 10 4.5 and temperature coefficient of resistivity (a) . 10.3%/°C were achieved using Mn and Al 2 O 3 :SiO 2 :TiO 2 (AST) additions. For x . 10, q max /q min . 10 3 and a . 8%/°C were only obtained in samples sintered in N 2 without subsequent air annealing. Complex impedance analysis revealed three relaxation processes, attributed to a semiconducting grain core, a PTC active grain boundary interface, and a grain boundary insulating layer. Local electrical activity was investigated by hot-stage conductive mode microscopy. The existence of symmetrical grain boundary electron beam-induced current and b-conductivity contrast at the grain boundaries, consistent with the presence of an electron trapping two-dimensional grain boundary plane, compensated by positive space charge layers and a low conductivity vacancy-rich layer, was revealed for the first time within this system.