A new method to determine organic and inorganic associations of trace elements in coal was devised using the ratio of concentrations for 34 elements in five vitrinite concentrates to the concentrations in companion whole-coal samples. Trace-element concentrations were determined by instrumental neutron activation analysis. The samples, all high volatile A (hvA) bituminous coal, were from five different coal beds: two from the Appalachian basin, West Virginia and Alabama, USA; two from the Pennine coalfield, England; and one from the Sydney Basin, Australia. The ash content (weight percent) of the vitrinite concentrates after combustion at 960 to 1,000 °C ranged from 0.6 to 1.3 percent, as compared to 2.5 to 7 percent in the whole coals. Most of the trace elements are enriched in the whole coal relative to the vitrinite concentrates, with some notable exceptions: (1) in the Australian coal, 12 of the 22 elements detected in both the whole-coal and the vitrinite concentrates are enriched in the vitrinite concentrates; (2) arsenic is enriched by 1.2 to 2.2 times in the concentrates in four of five coals; in the remaining coal, from West Virginia, arsenic is enriched in the whole coal by a factor of 22, and the iron is also enriched by a similar factor, which indicate that arsenic is associated with pyrite in this sample; (3) antimony is enriched in the vitrinite concentrates of the three foreign coal samples; (4) tungsten is enriched in the vitrinite concentrates of the four samples where tungsten was detected in both the concentrate and the whole coal; (5) the ash- and shale-normalized rare-earth element (REE) patterns suggest that some of the organic matter is enriched in REE.