This paper demonstrated a new approach for detecting pentosan content in wheat products enabled by phase‐transfer reaction technique. This approach was based on the phase‐transfer reaction of pentosans in wheat sample to furfural in an acidic medium. The hydrolysis reaction could be finished within 30 min at 90 °C, with a sulfuric acid concentration of 12.0 mol/L. The furfural generated from the hydrolysis of pentosan was then measured by headspace gas chromatography (HS‐GC) using a flame ionization detector (FID). The results showed that this method was precise (relative standard deviations (RSD)≤2.82 %) and accurate (relative differences (RD)≤6.49 % compared with the reference spectrophotometric method, the recoveries ranged from 98.1 to 102 %). Moreover, the developed approach is semi‐automated and efficient, which can be a good alternative method for the high‐throughput analysis of pentosan content in both laboratory and mill testing.