Geopolymers are an environmentally sustainable class of low-calcium alkali-activated materials (AAMs), distinct from high-calcium C-A-S-H gel systems. Synthesized from aluminosilicate-rich precursors such as fly ash, metakaolin, slag, waste glass, and coal gasification fly ash (CGFA), geopolymers offer a significantly lower carbon footprint, valorize industrial by-products, and demonstrate superior durability in aggressive environments compared to Ordinary Portland Cement (OPC). Recent advances in thermodynamic modeling and phase chemistry, particularly in CaO-SiO-AlO systems, are improving precursor selection and mix design optimization, while Artificial Neural Network (ANN) and hybrid ML-thermodynamic approaches show promise for predictive performance assessment. This review critically evaluates geopolymer chemistry and composition, emphasizing precursor reactivity, Si/Al and other molar ratios, activator chemistry, curing regimes, and reaction mechanisms in relation to microstructure and performance. Comparative insights into alkali aluminosilicate (AAS) and aluminosilicate phosphate (ASP) systems, supported by SEM and XRD evidence, are discussed alongside durability challenges, including alkali-silica reaction (ASR) and shrinkage. Emerging applications ranging from advanced pavements and offshore scour protection to slow-release fertilizers and biomedical implants are reviewed within the framework of the United Nations Sustainable Development Goals (SDGs). Identified knowledge gaps include standardization of mix design, LCA-based evaluation of novel precursors, and variability management. Aligning geopolymer technology with circular economy principles, this review consolidates recent progress to guide sustainable construction, waste valorization, and infrastructure resilience.