The increasing activity of wildland–urban interface (WUI) fires has raised concerns regarding the potential environmental and human health impacts of residual ash remaining after burning. In this study, we investigated the concentration and speciation of titanium in WUI fire ash. Total titanium concentrations in WUI fire ash ranged from 0.53 to 80 g kg^–1. Synchrotron-based macro- and microscale X-ray absorption near-edge structure (XANES and μXANES, respectively) spectroscopy were used to quantify the relative abundance of major Ti phases in the fire ash, and the results were corroborated by high resolution-transmission electron microscopy (HR-TEM) measurements. Rutile (α-TiO₂), anatase (β-TiO₂), ilmenite (FeTiO₃), and titanium(III) oxide (Ti₂O₃) were detected in all 20 ashes investigated by XANES and accounted for 0.26–0.83, 0.19–0.83, 0.33, and 0.17–0.72 of the spectral weight, respectively. Deeper analysis by μXANES of one sample demonstrated that Ti-bearing particles occurred as a mixture of rutile (α-TiO₂), anatase (β-TiO₂), ilmenite (FeTiO₃), and titanium(III) oxide Ti₂O_3, with the absence of a pure Ti₂O₃ phase. The presence of Ti₂O₃ in the WUI fire ash is ascribed to the reduction of rutile and anatase to Magnéli titania (Ti_nO_2n–1, n = 4–9), which is estimated to be the dominant phase of titanium in the 20 WUI fire ashes investigated by XANES. The occurrence of Magnéli titania was corroborated by HR-TEM. Our findings demonstrate the impact of WUI fires on titanium speciation; fires convert titanium dioxides (e.g., rutile and anatase) to reduced titanium phases (e.g., Magnéli titania). Based on HR-TEM analyses, most of the titanium-bearing particles were less than 500 nm in size. Magnéli particles have been shown to be more toxic than rutile and anatase and have been linked to reduced lung function. Therefore, this study provides critical insights into the pollution characteristics and potential health risks of WUI fire ashes and associated particles, which are currently poorly understood.