We describe the wartime challenges associated with the rapid developments in plutonium chemistry and metallurgy that were necessary to produce the core of the Trinity Device. Beginning with microgram quantities of plutonium metal late in 1943, initial measurements showed a wide and confusing variance in density and other properties. These confusing results were the first clues to the astounding complexity of plutonium. As this complexity was revealed, it introduced new challenges for the fabrication of kilogram-scale parts. In a remarkable period from January 1944 to June 1945, Manhattan Project scientists made rapid progress in understanding plutonium chemistry and metallurgy. By early 1945, they had discovered five of the six ambient-pressure phases of unalloyed plutonium and reported the density of these phases to within a value of 0.1 g/cm3 of those accepted today. They solved the stability problem introduced by these phases with a rapid alloy development program that ultimately identified gallium as the preferred element to stabilize the δ-phase, producing a plutonium alloy still of scientific and technical interest today. We conclude with a description of postwar developments in these areas, including applications of wartime plutonium metallurgy to civilian applications in nuclear reactors. We dedicate this paper to the memory of Ed Hammel, the Manhattan Project plutonium metallurgist whose previous description and documentation of plutonium history during the war has been essential in our research.