The geochemical characteristics of water produced from coalbed methane (CBM) wells contain rich information about the associated geology, environment, and production. This study was conducted in the Southern Qinshui Basin, where produced water samples were collected from 10 typical CBM wells and their ionic compositions and water quality parameters were tested. The differences in the chemical characteristics of the produced water between different producing coal seams and between single-seam production wells (SPWs) and multi-seam co-production wells (MCWs) were compared, and the geochemical formation process of the produced water was revealed. The following conclusions were obtained: (1) the water produced samples that were mainly Na-HCO3-type and were generally weakly alkaline and moderately mineralized. The water produced from No. 15 coal seam was more enriched in SO4, Ca, and Mg compared to that of No. 3 coal seam, and the variations were more intense, reflecting a more complex water chemistry formation. (2) The ionic data of the water produced from MCWs do not lie between the coal seams of SPWs, nor do they satisfy the linear relationship between the ionic compositions of SPWs, reflecting the differences in the water sources between MCWs and SPWs. Water from MCWs tends to communicate with active water sources outside the coal seams, and the produced water contains small amounts of Cl and total dissolved solids, thus inhibiting the pressure reduction efficiency and limiting the effect of CBM co-production. (3) Based on a principal component analysis of the ionic compositions, two characteristic components were extracted, and these represented two types of hydrochemical formation processes. The first type is pyrite oxidation and carbonate dissolution, and its opposite represents sulfate reduction. The second type reflects the groundwater retention and confinement characteristics, and its opposite represents active groundwater or stronger recharge conditions. (4) A geochemical formation model of the water produced from CBM wells in the study area was constructed. Cation exchange adsorption and sulfate reduction were found to be the main water–rock interactions in the coal measure, and they determine the overall water quality of the produced water. Recharge has a relatively significant influence on water produced from MCWs. Pyrite oxidation exists in the water produced from No. 15 coal seam of the Taiyuan Formation, and the higher sulfur content in the coal contributes to this reaction. The results of the study will assist in deepening our understanding of the geochemical formation mechanisms of water produced from CBM wells, and they provide the main reasons for the poor CBM co-production effect from the Shanxi and Taiyuan Formations.