Serial dual-emitting single crystals LiYF4: 0.5Ce3+/αMn2+ (α = 0, 0.05, 0.1, 0.3, 0.5, and 1.0) samples were synthesized by a reformative Bridgman technique. A comprehensive investigation was carried out to systematically analyze the crystal structure, energy transfer mechanism, luminescence properties, and temperature-dependent sensing capabilities. The single crystal exhibits distinct dual broadband emissions, with peaks at 373 nm attributed to the transition from 5d to 4f of Ce3+ ions and 555 nm assigned to the transition from 4T1g(4G) to 6A1g(4S) level of Mn2+ ions. The optical properties of the Ce3+/Mn2+ co-doped LiYF4 single crystal were studied in relation to temperature, with a focus on enabling precise optical temperature measurements. The research revealed a relative sensitivity of 0.995 % K−1 at 498 K and temperature resolution of 0.03 K at 498 K, indicating the potential of LiYF4: Ce3+/Mn2+ single crystals for use in highly sensitive optical thermometry applications. These findings highlight the crystal suitability for the development of temperature sensing devices with enhanced sensitivity and resolution.