South Africa is endowed with a wealth of coal-fired power stations that can produce extremely high volumes of fly ash per year exceeding 34 million tonnes. The use of high-volume fly ash (HVFA) binders in the construction sector has the capacity to significantly reduce greenhouse gas emissions associated with traditional cement production and offset the carbon footprint of Eskom. The excessive production of fly ash by Eskom warrants the need for developing ultra-high-volume fly ash binders (UHVFA, fly ash/binder > 60 wt%). Nonetheless, fly ash (FA) replacement of cement is still largely limited to 35% regardless of more ambitious research indicating the potential to surpass 60%. In view of the urgent need for South Africa to offset and reduce its carbon footprint, this work reviews and summarises the literature on the performance of HVFA binders with a focus on two specific areas: (i) strength and (ii) durability. On HVFA binder strength, the focus is drawn on work that analysed the compressive strength, flexural strength, and split tensile strength. This review focuses on the extant literature analysing the durability of HVFA binders using various tests, including sorptivity, resistivity, permeability, tortuosity, rapid chloride penetration tests, resistance to sulphate attack, and microstructural analysis. As the FA content increases towards optima, i.e., 50–80%, the most indicative composite characteristics of the strength and durability properties are UCS (30–90 MPa) and permeability (low). This review reveals the leading methodologies, instrumentation, findings, challenges, and contradictions.