An online thermogravimetric measurement method of ash deposition was developed. Ash deposition and slag bubble in the reductive zone of pulverized coal staged combustion were investigated. Firstly, a steady pulverized coal staged combustion was achieved in an electrically heated down-fired furnace. Additionally, gas species, coal conversion, and particle size distribution were quantitatively measured. Secondly, real-time ash deposition rates at different temperatures (1100–1400 °C) were measured, and deposition samples were carefully collected with an N₂ protection method. The morphologies of collected samples were investigated through a scanning electron microscope. It was found that the deposited ash transformed from a porous layer composed of loosely bound particles to a solid layer formed by molten slag. Different behaviors of the slag bubble were observed, and bubble sizes were significantly affected by the deposition temperature. A deposition and bubble formation mechanism was proposed and used for modeling. Results showed that the proposed model well predicted the observed ash deposition and bubble formation process.