Recent advances in the use of positron annihilation to study defect ensembles in and on the surfaces of metals, are pointing the way towards studies where particular positron-electron annihilation modes may be identified and studied in the presence of one another. Although a great deal is understood about the annihilation of positrons in ostensibly defect-free metals, much less is understood when the positron annihilates in complex defect systems such as liquid metals, amorphous solids, or at or near the vacuum-solid interface. In this paper the results of three experiments, all of which demonstrate means by which we can resolve various poistron annihilation channels from one another, are discussed