Luminescence of monoclinic lithium metatitanate (Li2TiO3) powders activated with different quantities of Mn4+ is studied in detail. Its strong deep‐red emission arising from the Mn4+ 2Eg → 4A2g spin forbidden transition is centered at around 688 nm and is suitable for luminescence thermometry. Structural and electron paramagnetic resonance analyses show that Mn4+ ions are equally distributed in two almost identical Ti4+ sites in which they are octahedrally coordinated by six oxygen ions. Calculations based on the exchange charge model of the crystal field provided values of Racah parameters (B=760 cm−1, C= 2993 cm−1), crystal‐field splitting Dq= 2043 cm−1, and the nephelauxetic parameter β1=0.9775. The maximal quantum efficiency of 24.1% at room temperature is found for 0.126% Mn4+ concentration. Temperature quenching of emission occurs by a cross‐over via 4T2 excited state of the Mn4+ ions with T1/2=262 K and is quite favorable for the application in the lifetime‐based luminescence thermometry since relative changes in emission decay values are exceptionally‐large (around 3.21% at room temperature). We derived theoretical expressions for the temperature dependence of the absolute and relative sensitivities and discuss the influence of host material properties on lifetime sensitivities. The luminescence of Mn4+ activated Li2TiO3 deep‐red phosphor provides the high‐performance temperature sensing with temperature resolution better than 30 mK over the wide temperature range. The engineering of the Mn4+ activated materials for the high‐precision luminescence thermometry via the control of the energies of 4T2g level and phonon coupling is shown.