The global vanadium (V) demand in industry increased 8% from 2006 to 2014, which will become 3.45% higher in next decade. The burgeoning V demand leads to potential risks to environment quality and human health than before. However, only 5 countries currently regulate the guideline of soil V (42-180 mg/kg) excluding Taiwan. Geochemical fractionation is crucial to the solubility of V in soils, this study attempted to explore the fractions of soil V for the baseline of V from 17 pedons with 94 horizon samples throughout Taiwan. These pedons were selected from different soil parent materials comprising slate, sandstone and shale, andesite, serpentine, and basalt. The fractionation of V in all soil horizons was assessed using BCR sequential extraction technique. The total V concentration was analysed using portable x-ray fluorescence (pXRF) in situ and ICP-AES followed with HF-digestion in the lab. The total V concentration by ICP in the soils from Taiwan ranged from 35.4 to 475 mg/kg and the average level was 182 mg/kg. Moreover, the total V concentration in the basalt-derived soils was much higher than sandstone-derived soils. Nevertheless, the weathering degree of soil did not clearly affect the V level between pedons. Furthermore, V concentration obtained by pXRF was significantly and positively correlated with that by ICP, demonstrating pXRF was feasible alternative to determine V in the field for rapid screening of V. The results of BCR sequential extraction indicated V was primarily fixed in the mineral lattices, while Fe/Mn-oxide-bounded fraction was also observed. Thus, DCB extraction was conducted and demonstrated that V was mainly associated with Fe/Mn oxides.