Indexes of fluoride ions and total dissolved solids from 73 samples in shallow groundwater in Huaibei Plain, Anhui Province were measured. And the characteristics of spatial variation are analyzed by mathematical methods of statistics and geostatistics. The results show that: 1) fluoride ions (F-) and total dissolved solids (TDS) obey the logarithmic normal distribution. The coefficients of variation were 0.77 and 0.36, respectively; 2) the fluoride ions and total dissolved solids from groundwater satisfy the Gaussian semi-variogram model and exponential model respectively. Fluoride ions have an autocorrelation in the 49.00 km. Total dissolved solids have an autocorrelation in the 7.21 km; and 3) the zone with concentration of fluoride ions >1 mg/L is located in the northeast and central region of Huaibei Plain. The zone with concentration of total dissolved solids >1 g/L lies mainly in Suzhou and Huaibei cities in the Huaibei Plain. The spatial distribution characteristics of total dissolved solids are similar with those of fluoride ion.