The tungsten bronze-type lead metaniobate (PbNb2O6, PN) is a promising material for high-temperature piezoelectric devices, while its application is limited by the difficulty in fabrication. In this study, the microstructure and electrical properties of Ca-doped PN and Ca, Mn-co-doped PN ceramics sintered at different temperatures were investigated. Doping promoted the formation of the originally metastable ferroelectric orthorhombic phase. This might be partly attributed to the increased lattice distortion of the orthorhombic phase in the doped samples compared to that reported for pure PN. However, in single A-site Ca-doped PN the ferroelectric orthorhombic structure showed a low stability and started to transform to paraelectric phase far below 300 degrees C, resulting in unstable high temperature piezoelectric properties. Interestingly, such a phase transition was completely depressed by A-site Ca and multisite Mn-co-doping, which also improved the piezoelectric performance (d(33)=71pC/N) and thermal stability in both structure and piezoelectricity. The better stability and performance of the co-doped samples were explained by the improved sintering behavior and poling efficiency as well as its ability to occupy different sites in the TTB lattice.