Recent images of the surface of Mercury have revealed an unusual and intriguing landform: sub-kilometre scale, shallow, flat-floored, steep-sided rimless depressions typically surrounded by bright deposits and generally occurring in impact craters. These ‘hollows’ appear to form by the loss of a moderately-volatile substance from the planet’s surface and their fresh morphology and lack of superposed craters suggest that this process has continued until relatively recently (and may be on-going). Hypotheses to explain the volatile-loss have included sublimation and space weathering, and it has been suggested that hollow-forming volatiles are endogenic and are exposed at the surface during impact cratering. However, detailed verification of these hypotheses has hitherto been lacking.In this study, we have conducted a comprehensive survey of all MESSENGER images obtained up to the end of its fourth solar day in orbit in order to identify hollowed areas. We have studied how their location relates to both exogenic processes (insolation, impact cratering, and solar wind) and endogenic processes (explosive volcanism and flood lavas) on local and regional scales. We find that there is a weak correlation between hollow formation and insolation intensity, suggesting formation may occur by an insolation-related process such as sublimation. The vast majority of hollow formation is in localised or regional low-reflectance material within impact craters, suggesting that this low-reflectance material is a volatile-bearing unit present below the surface that becomes exposed as a result of impacts. In many cases hollow occurrence is consistent with formation in volatile-bearing material exhumed and exposed during crater formation, while in other cases volatiles may have accessed the surface later through re-exposure and possibly in association with explosive volcanism. Hollows occur at the surface of thick flood lavas only where a lower-reflectance substrate has been exhumed from beneath them, indicating that this form of flood volcanism on Mercury lacks significant concentrations of hollow-forming volatiles.