In this paper, a detailed study of the Er/Yb/W tri-doped BaBi2-x-yNb2-zErxYbyWzO9 (BBN) system and a comparison of undoped, Er-doped, Er/Yb co-doped and Er/Yb/W tri-doped BBN systems are presented. All the BBN ceramics are prepared using the solid-state approach. The XRD spectra demonstrated that each BBN composition has an orthorhombic geometry. The UCL spectra are traced at 980 nm and exhibit two distinctive green bands and one red band at 535 nm, 556 nm, and 673 nm, respectively. The UCL intensity improves with W6+ concentration and reaches a maximum at (z = 0.02); after this concentration, the quenching effect occurs. The pump power variation on UCL spectra confirmed the involvement of two photons. The time-resolved fluorescence analysis was done for green and red emissions, and it was observed that the time decay increased for higher dopant concentrations, suggesting a non-radiative transition at higher dopant concentrations. The FIR technique measured the absolute sensitivity and had a value of 0.91 % K−1 at 573 K. These improvements suggest that the prepared material may help develop advanced electronic equipment for multifunctional applications.