The first MESSENGER flyby of Mercury obtained images of 21% of the surface not seen by Mariner 10, including the center and western half of the Caloris basin and regions near the terminator that show details of the nature of smooth and intercrater plains. These new data have helped to address and resolve a series of longstanding questions on the existence and nature of volcanism on Mercury and the distribution of volcanic materials. Data from the Mercury Dual Imaging System (MDIS) on the MESSENGER spacecraft have shown the following: (1) Numerous volcanic vents, in the form of irregularly shaped rimless depressions, are concentrated around the interior edge of the Caloris basin. (2) These vents appear to be sources for effusive volcanism that in one case built a shield in excess of 100 km in diameter and in some cases formed bright haloes around the vents that are interpreted to represent pyroclastic eruptions. (3) Lobate margins of plains units, seen previously in Mariner 10 data, are documented in MESSENGER images with more clarity and are often distinctive in morphology and color properties, supporting the interpretation that these features are the edges of lava flow units. (4) The interior of the Caloris basin is filled with plains units spectrally distinctive from the rim deposits, and comparison with the lunar Imbrium basin and superposed impact crater stratigraphy provide evidence that these units are volcanic in origin; detailed differences in the mineralogy of lava flow units, so prominent in Imbrium, are not seen in the Caloris interior. (5) Some of the smooth plains surrounding the exterior of the Caloris basin show distinct differences in color and morphological properties, supporting a volcanic origin. (6) Some smooth and intercrater plains units distant from the Caloris basin show evidence of flooding and embayment relations unrelated to Caloris ejecta emplacement; local and regional geological and color relationships support a volcanic origin for these plains. (7) Large impact craters show a sequence of embayment of interior floor and exterior ejecta deposits that supports a volcanic origin for the embayment and filling processes. (8) Crater embayment and flooding relationships in selected areas suggest volcanic plains thicknesses of many hundreds of meters and local thicknesses inside impact craters of up to several kilometers. (9) Impact crater size–frequency distributions for Caloris exterior deposits, including the facies of the Caloris Group and relatively high- and low-albedo smooth plains, show that they are younger than plains interior to Caloris and thus must be dominantly the product of post-Caloris volcanism. These new data provide evidence that supports and confirms earlier hypotheses from Mariner 10 data that volcanism was important in shaping the surface of Mercury. The emerging picture of the volcanic style of Mercury is similar to that of the Moon, the other small, one-plate planetary body: there are no major shield volcanoes (e.g., comparable to Tharsis Montes on Mars), shallow magma reservoirs are rare, and there is little evidence for surface deformation or long-lived volcanic sources related to sites of upwelling mantle. The close association of volcanic plains and surface deformation features suggests that future observations and analyses can help document the relation between the volcanic flux and the evolving state and magnitude of stress in the lithosphere of Mercury.