Fonio (Digitaria exilis Stapf) is an ancient African cereal that represents a rich source of carbohydrate, fat, fiber, vitamins, minerals, and sulfur-containing amino acids. Processing and utilization of fonio require adequate knowledge of its structural, chemical, and nutritional characteristics. The present work evaluates the structural, techno-functional, and gelling properties of fonio and compares them to other major gluten-free cereals (rice, maize, sorghum, and millet). Fonio flour presented significantly higher water absorption index and swelling power, while it scored a lower water solubility index than the reference flours. The pasting viscosity profile of fonio was similar to that of rice, with equivalent peak viscosity but a breakdown viscosity 24% lower than rice, indicative of higher stability and resistance to shearing and heating. Rheological properties demonstrated that fonio generates gels with remarkably strong structures. At 15% concentration, fonio gel withstood stress 579% higher than those observed in the reference flours without breaking its structure. Fonio flour presented the highest gelatinization enthalpy (11.45 J/g) and a narrow gelatinization temperature range (9.96 °C), indicative of a better-packed starch structure than the other analyzed flours. The texture of the gels made with fonio showed higher firmness over the evaluated period. These combined results suggest that fonio is a suitable ingredient for gel-like food formulations.