In this study, headspace gas chromatography–ion mobility spectrometry, headspace gas chromatography–mass spectrometry, and lipidomics were used to explore the effects of three oil temperatures (210 °C, 180 °C, 150 °C) with single- and traditional triple-oil-splashing processes (210 °C → 180 °C → 150 °C) on the formation of key chili oil aromas. A total of 31 key aroma compounds were identified, with 2,4-nonadienal, α-pinene, α-phellandrene, and β-ocimene being found in all treatment groups. Lipidomics suggested that oleic acid, linoleic acid, and α-linolenic acid were highly positively correlated with key chili oil key aroma compounds, such as (E)-2-heptenal, 2-methylbutyraldehyde, limonene, (E, E)-2,4-heptadienal, 2,4-nonadienal, and 2,4-decadienal. The temperature and frequency of oil splashing significantly affected the chili oil aroma profile (p < 0.05). The citrus, woody, and grassy notes were richer in chili oil prepared at 150 °C, malty and fatty aromas were more prominent at 180 °C, and the nutty aroma was stronger in 210 °C prepared and triple-splashed chili oil. The present study reveals how sequential oil splashing processes synergistically activate distinct lipid degradation pathways compared to single-temperature treatments, providing new insights into lipid-rich condiment preparation, enabling chefs and food manufacturers to target specific aroma profiles.