Recognizing the nature and formation progress of the ash deposits is essential to resolve the deposition problem hindering the wide application of large-scale biomass-fired boilers. Therefore, the ash deposits in the superheaters of a 220 t/h biomass-fired CFB boiler were studied, including the platen (PS), the high-temperature (HTS), the upper and the lower low-temperature superheaters (LTS). The results showed that the deposits in the PSs and HTSs were thin (several millimeters) and compact, consisting of a yellow outer layer and snow-white inner layer near the tube surface. The deposits in the upper LTS appeared to be toughly sintered ceramic, while those in the lower LTS were composed of dispersive coarse ash particles with an unsintered surface. Detailed characterization of the cross-section and the initial layers in the deposits revealed that the dominating compositions in both the PSs and the HTSs were Cl and K (approximately 70%) in the form of KCl. Interestingly, the cross-section of the deposition in the upper LTS exhibited a unique lamellar structure with a major composition of Ca and S. The contents of Ca and Si increased from approximately 10% to approximately 60% in the deposits from the high temperature surfaces to the low temperature ones. It was concluded that the vaporized mineral matter such as KCl played the most important role in the deposition progress in the PS and the HTS. In addition, although the condensation of KCl in the LTSs also happened, the deposition of ash particles played a more important role.