Red emission of the Mn⁴⁺ ions incorporated in different materials is used in various applications, such as lighting, holographic recording, thermoluminescence dosimetry, thermometry, etc. Mn⁴⁺ emission can improve color-rendering-index of phosphor-converted white-light-emitting diodes, and it is a promising candidate to replace the well-established rare-earth Eu activator in red phosphors. Here, synthesis, structure, detailed spectroscopic and crystal field analysis of Mn⁴⁺ doped Li₂TiO₃ are presented. We have successfully synthesized Li₂Ti_0.995Mn_0.005O₃ powder by a solid state synthesis. All precursors were mixed with stoichiometric ratio Li : Ti = 2 : 1 and calcined at 800⁰C for 5 h to produce pure-phase. Structural analysis was done by X-ray diffraction. It confirmed monoclinic Li₂TiO₃ structure with space group C2/₂, in which the octahedral sites are occupied by Ti⁴⁺ and Mn⁴⁺. Optical characterization included measurements of photoluminescence excitation and emission spectra, emission decay analyses and diffuse reflection measurements. Optical spectra showed emission and absorption bands originating from d–d electronic transitions (d³ configuration). Kubelka-Munk function of the measured diffuse reflectance spectrum showed characteristic absorption of Mn⁴⁺. Deep red emission at 680 nm under λ_exc= 490 nm is a result of the spin-forbidden ²Eg→⁴A₂ and ⁴T₂→ ⁴A₂ electron transition of the tetravalent manganese ions. The energy levels of the Mn⁴⁺ ions in Li₂TiO₃ were calculated using the crystal field exchange-charge model. Three parameters are needed to describe completely each energy level: the Racah parameters B and C, which determine the positions of the free ion energy levels, and the crystal field strength denoted by Dq, which describes the splitting of the free ion terms. These parameters were calculated and showed good agreement with the experimental photoluminescence excitation and emission spectra.