The Er3+ doped Bi5TiNbWO15 ceramics have been synthesized using conventional solid-state reaction techniques. The crystal structure, ferroelectric properties, UC emission properties and especially the temperature sensing behaviors were systematically studied. With increasing Er3+ content, the investigation of XRD pattern, the ferroelectric loop and the UC emission indicated that the Er3+ ions dopants preferentially substituted the A sites of Bi3TiNbO9 and then Bi2WO6. Based on fluorescence intensity ratio (FIR) technique, the observed results implied the ceramics were promising candidates for temperature sensors in the temperature range of 175 K −550 K. More importantly, this study provided a contrast of temperature sensitivity between emission from the same part (Bi3TiNbO9) in bismuth layered-structure and emission from the different part (Bi3TiNbO9 and Bi2WO6) in bismuth layered-structure for the first time.