The elusiveness of reactive free radicals poses great challenges for their investigation per se in most processes in which they have an intermediary role; this is true particularly in heterogeneous media. There are, however, methods available for the detection of radicals with enormous sensitivity and specificity which are given the collective acronym mSR (MuSR). All the MuSR methods rely upon the addition of the light hydrogen atom 'muonium' -a hydrogen atom with a radioactive positive muon as its nucleus, having a mass 1 9 that of a protium atom -to an organic substrate. In addition to its property of radioactive decay, the muon also has spin, and therefore experiments akin to those of conventional magnetic resonance experiments may be undertaken. Among the suite of methods thus encompassed is transverse-field MuSR (TF-MuSR), which is equivalent to ENDOR and yields the nucleus (muon) coupling directly, while the avoided level crossing (ALC) approach yields the magnitudes of the couplings from other nuclei present in a given radical, and also their relative signs (like TRIPLE does). Although these are resonance experiments, they do not require the application of external radiofrequency fields; however, radiofrequency experiments are possible, in which the analogies with more conventional magnetic resonance experiments are more direct. However, the experiments which are rendered possible by muons are unique, and have no practicable counterpart in more conventional techniques. In particular, the feature of single-particle-counting methods being used in combination with nuclear spins which are 100% polarised (i.e. vastly in excess of the Boltzmann factor!) permits unparalleled sensitivity regarding reactive radicals. Through the incisiveness of these methods, knowledge in the field of free radical chemistry has been gained that would be unachievable using the more established methods of EPR and its relatives.In consequence of these benefits, although my own background is in EPR (a topic which I have reviewed previously in this series), 1-3 my research group has become increasingly involved in the techniques of MuSR, especially in regard to determining the behaviour of radicals in catalytic systems and in heterogeneous environmental processes, and for the measurement of free radical reaction rates pertinent to biological membrane damage and repair. These are all topics whose investigation we could not have attempted without muons.