High-alumina-coal fly ash (HAFA) with a high Li content is regarded as a potential resource for Li production. To support the development of Li recovery technology from HAFA, the distribution and modes of occurrence of Li in HAFA were investigated. HAFA was separated into magnetic particles, glass, and mullite + corundum + quartz (MCQ) using an add-alkali combination method. 79-94% of the Li was found in glass, with the remaining 5-16% and < 5% of Li in MCQ and magnetic particles, respectively. Chemical state imaging of Li in HAFA, magnetic particles, and MCQ was obtained using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Lithium was found to be relatively uniformly distributed in the HAFA particles and strongly correlated with Al and Si. Possible formation pathways of Li in the glass phase were proposed. The energy differences between reactants and products (Delta E) calculated using the generalized gradient approximation (GGA) method indicated that Li occurred in Q(3)(0Al) and Q(3)(1Al) structures by reacting with Q(4)(0Al) and Q(4)(1Al). Based on the experimental and simulation results, we propose extracting Li during the pre-desilication process by dissolving the glass phase.