The concentration, modes of occurrence and geological origin of beryllium in five workable coal beds from the Pu’an Coalfield of Guizhou were studied using the inductively coupled-plasma mass spectrometry (ICP-MS), floating and sinking experiments (FSE) and sequential chemical extraction procedures (SCEP). The results show that the average concentration of beryllium in coals from the Pu’an Coalfield is 1.54μg/g, much lower than that in most Chinese and worldwide coals. Beryllium in the Pu’an coals was not significantly enriched. However, it should be noted that the No. 8 coal bed from the study area has a high concentration of beryllium, 6.89μg/g, three times higher than the background value of beryllium in coal. Beryllium in coal mainly occurs as organic association and has predominantly originated from coal-forming plants when its concentration is relatively low. The concentration of beryllium occurring as organic association is close to that distributed in inorganic matter when beryllium concentration of coal is similar to its background value, and in addition to coal-forming plants, beryllium is mainly derived from detrital materials of terrigenous origin. When beryllium is anomalously enriched in coal, it mainly occurs as organic association and is derived from volcanic tonsteins leached for a long geological time and then adsorbed by organic matter in peat mire.