The use of selective pre-concentration and differential pulse anodic stripping voltammetry (DPASV) using a carbon paste electrode modified (CPEM) with spinel-type manganese oxide has been proposed for the determination of lithium ions content in natural waters. The new procedure is based on the effective pre-concentration of lithium ions on the electrode surface containing spinel-type Mn(IV) oxide with the reduction of Mn(IV) to Mn(III) and consequently the lithium ions intercalation (insertion) into the spinel structure. The best DPASV response was reached for an electrode composition of 25% (m/m) spinel-type MnO(2) in the paste, 0.1moll(-1) tris(hydroxymethyl)aminomethane (TRIS) buffer solution of pH 8.3, scan rate of 5mVs(-1), accumulation potential of 0.3V versus saturated calomel reference electrode (SCE), pre-concentration time of 30s and potential pulse amplitude of 50mV. In these experimental conditions, the proposed methodology responds to lithium ions in the concentration range of 2.8x10(-6) to 2.0x10(-3)moll(-1) with a detection limit of 5.6x10(-7)moll(-1). The determination of the lithium ions content in different samples of natural waters samples using the proposed methodology and atomic absorption spectrophotometry are in agreement at the 95% confidence level and within an acceptable range of error.