Aimed at the rainfall-runoff tracing using inorganic ions, the experimental study is conducted in the Chuzhou Hydrology Laboratory with special designed experimental catchments, lysimeters, etc. The various runoff components including the surface runoff, interflow from the unsaturated zone and the groundwater flow from saturated zone were monitored hydrometrically. Hydrochemical inorganic ions including Na+, K+, Ca2+, Mg2+, Cl-, SO42-, HCO3- + CO32-, NO3-, F-, NH4-, PO42-, SiO2 and, pH, EC, 18O were measured within a one month period for all processes of rainfall, various runoff components and groundwater within the catchment from 17 boreholes distributed in the Hydrohill Catchment, few soil water samples were also included. The results show that: (a) all the runoff components are distinctly identifiable from both the relationships of Ca2+ versus Cl-/SO42-, EC versus Na+/(Na+ + Ca2+) and, from most inorganic ions individually; (b) the variation of inorganic ions in surface runoff is the biggest than that in other flow components; (c) most ions has its lowermost concentration in rainfall process but it increases as the generation depths of runoff components increased; (d) quantitatively, ion processes of rainfall and groundwater flow display as two end members of that of other runoff components; and (e) the 18O processes of rainfall and runoff components show some correlation with that of inorganic ions. The results also show that the rainfall input is not always the main source of inorganic ions of various runoff outputs due to the process of infiltration and dissolution resulted from the pre-event processes. The amount and sources of Cl- of runoff components with various generation mechanisms challenge the current method of groundwater recharge estimation using Cl-.