The extraction system contains secondary amides and alkyl alcohols which are separately used as the extractants for extracting lithium and boron and consist of a single compound or a mixture of two or more compounds, and the total number of carbon atoms in their molecules are 12˜18 and 8˜20 respectively; the extraction system has a freezing point less than 0° C. With a volume ratio of an organic phase and a brine phase being 1˜10:1, at a brine density of 1.25˜1.38 g/cm3, at a brine pH value of 0˜7 and at a temperature of 0˜50° C., a single-stage or multi-stage countercurrent extraction and a stripping are conducted to obtain a water phase with a low magnesium-lithium ratio, which is subjected to concentration, impurity removal and preparation to get lithium chloride, lithium carbonate, lithium hydroxide and boric acid respectively. Water is used for stripping, greatly reducing the consumption of acid and base.