⁶Li/⁷Li isotopic ratio was determined in lithium based compounds and refractory materials by TIMS using a novel approach. The method involved fusion of the samples such as Lithium Aluminate (LiAlO₂), Lithium Titanate (Li₂TiO₃), Lithium Carbonate etc, with Sodium Borate flux directly on the loading filament to produce NaLiBO₂⁺ ions at m/z 71,72 and 73 and Na₂BO₂⁺ at m/z 88 and 89. ⁶Li/⁷Li was determined by monitoring NaLiBO₂⁺ ions at m/z 71, 72 and 73. Contributions from isotopes of boron to the ion intensity at m/z 71–73, were accounted by sequentially monitoring Na₂BO₂⁺, at m/z 88 and 89 during same analysis. L-SVEC Li₂CO₃was used for the initial investigations to identify the optimum composition of the analyte, sodium borate mixture required for obtaining precise ⁶Li/⁷Li ratio and the possible ion formation mechanism. Fusion of the lithium compounds with boron rich sodium borates having compositions such as Na₂O·5B₂O₃ and Na₂O·10B₂O₃ resulted in strong and stable molecular ion intensities for both NaLiBO₂⁺ and Na₂BO₂⁺. Average ⁶Li/⁷Li isotopic ratio obtained for L-SVEC lithium from ten measurement using this technique was 0.08277 ± 0.00006 (S.D). Refractory compounds Li₂TiO₃ and LiAlO₂ and lithium salts such as Li₂CO₃ (lithium source for the refractory compounds) and Li₂B₁₀O₁₆ were analysed for ⁶Li/⁷Li isotopic ratio with precision of better than 0.07% (% R.S.D). Agreement between the ⁶Li/⁷Li isotopic ratio of the refractory compound and the starting material signified that there is no matrix induced mass bias. This technique not only resulted precise values for ⁶Li/⁷Li isotopic ratio but has also simplified the procedure for isotopic analysis of Li in refractory materials by circumventing the dissolution and purification step that would have been otherwise required for established mass spectrometric methods.