Biochar (BC) is a carbonaceous material obtained by pyrolysis at 200−1000 °C in the limited presence of O2 of different vegetable and animal biomass feedstocks. BC has demonstrated great potential, mainly in environmental applications, due to its high sorption ability and persistent free radicals (PFRs) content. These characteristics enable BCs to carry out the direct and PFRs-mediated removal/degradation of environmental organic and inorganic contaminants. The types of PFRs possibly present in BC depend mainly on the pyrolysis temperature and the kind of pristine biomass. Since they also can cause ecological and human damage, a systematic evaluation of the environmental behavior, risks, or management techniques of BC-derived PFRs is urgent. PFRs generally could consist of a mixture of carbon- and oxygen-centered radicals, and of oxygenated carbon-centered radicals, depending on the pyrolytic conditions. Here, to promote a more productive and beneficial use of BC and related PFRs and stimulate further studies to make them environmentally safer and less hazardous to humans, we have first reviewed the most common methods used to produce BC, its main environmental applications, the primary mechanisms by which BC remove xenobiotics, as well as the reported mechanisms for PFRs formation in BCs. Secondly, we have discussed the PFRs environmental migration and transformation; we have reported the main PFRs-mediated applications of BCs to degrade inorganic and organic pollutants, the correlated environmental potential risks, and the possible strategies to limit them.