Coal fly ash (CFA) contains considerable amounts of potentially hazardous trace elements. Characterization of trace elements in CFA is essential for the safe disposal and recycle of CFA. The objectives of this study were i) to determine and predict the solubility of trace elements in CFA in relation to their chemical and mineralogical properties, and ii) to characterize trace elements using the surface chemical analysis including time-of-flight secondary ion mass spectrometry (TOF-SIMS) and accelerator-based micro particle induced X-ray emission (PIXE) analysis, in combination with X-ray absorption fine structure (XAFS) spectroscopy with a primary focus on As and Cr. The CFA samples from 12 thermal power plants contained B (ave. 203 mg kg−1), F (90 mg kg−1), Cr (63 mg kg−1), As (21 mg kg−1), and Se (3.2 mg kg−1), in which the water soluble fraction relative to the total concentration decreased in the order B (24 %) > Se (23 %) > F (20 %) > As (1.7 %) > Cr(IV) (0.71 %). A regression model indicated that water extractable As and Cr(VI) from CFA increased linearly with increasing SiO2 and CaO in CFA, respectively. The SIMS images showed that B was finely and heterogeneously distributed on CFA, whereas F was distributed homogeneously on CFA. The combined results from micro-PIXE and XAFS revealed that i) As was distributed on about 50-μm particles in the form of As(V) associated with Al and Ca, and ii) Cr was co-located with Fe and Ca on about 50-μm particles and was present as Cr(III). This study demonstrated that the combined results from TOF-SIMS, micro-PIXE, and XAFS techniques enable trace elements in CFA to be better characterized in terms of spatial distribution and chemical speciation.