Substructure development through aging and annealing treatments was studied for rapidly solidified TiCo ribbons using TEM. In as-spun ribbons, equiaxed grain structure was developed and its crystal structure was B2-ordered immediately after melt-spinning, while a small amount of fine precipitates existed as second phase. Some grains were dislocation-free but others contained a certain amount of curved or helical dislocations and loops. The dislocation density in the ribbons annealed at 700 °C for 24 h was obviously higher than those in the as-spun ribbons and the ribbons aged at 200 °C for 100 h. The increase of the dislocation density in the annealed ribbons would result from the absorption of excess vacancies. Therefore, the obtained results indicated that a large amount of supersaturated thermal vacancies were retained in TiCo as-spun ribbons by the rapid solidification.