Accurate determination of lithium (Li)isotopic composition in natural geological samples is the basis for Li isotope geochemical studies. In this study, a method contained preparation of geological materials (water and rock) and accurate determination of Li isotopic composition was set up. The separation of Li from water and rock samples was implemented by a single column containing 1.5 mL of Bio-Rad AG 50W-X12 (200–400 mesh) resin, with 0.40 M HCl and 1.0 M HCl as eluents. Only 8.5 and 14 mL of eluents were used to separate Li from water and rock samples with this method, respectively. Blank signal of the operation procedure was (2.4 ± 0.1) mV, which was almost same as the 2.3 mV of the 2% HNO₃ signal used in this study. Experimental results showed that Li isotopic fractionation during leaching process was significant and deviation of δ⁷Li values in these samples with incompletely recovered Li reached up to 50‰. Lithium isotopic ratios were determined by multi-collector ICP-MS (Nu Plasma II) using the sample standard bracketing (SSB) method. L-SVEC standard with similar Li concentration to samples (about 80 ng mL⁻¹) was used in this study. The external precision (2σ) of this technique, determined by repeated measurement of pure Li standard solutions and seawater was < ±0.8‰. The measured δ⁷Li values of seawater and rock standards AGV-2, BCR-2 and GSP-2 were +31.4‰ ± 0.7‰ (n = 18), +7.23‰ ± 0.16‰ (n = 4), +3.7‰ ± 0.7‰ (n = 8) and −0.10‰ ± 0.18‰ (n = 4), respectively, similar to previously published values. This method could be used to accurately determine Li isotopic composition of various types of geological samples such as waters and rocks. The advantage of this method was that the amount of resin and reagent was reduced to 50% or less of the previous studies, thereby significantly improving the work efficiency and reducing the operation procedure blank.