A novel method based on flow injection analysis (FIA) and flame atomic emission spectrometry (FAES) is presented. It was developed for direct determination of barium in drinking water, in natural water, in digested samples of bone and liver, in saline water and in a standard reference material (NIST SRM 1640). It was found that digestion of bone by an incineration procedure was required, in order to extract most of the barium. In the FIA manifold, barium was pre-concentrated by co-precipitation with lead chromate leading to a crystalline deposit that adhered well to the inner walls of a nylon knotted reactor (KR). The method documents a novel example of formation of a crystalline compound during the pre-concentration step. The method comprises filterless pre-concentration by co-precipitation that proceeds successfully in a FIA system. An enrichment factor (EF) of 24 was achieved under normal working conditions at a sampling frequency of 50 h(-1). The detection limit (LOD, 3sigma) was determined as 0.8 mug L-1 and species of iron(II) and iron(III) constituted the main species of interference.