Piper longum L. (long pepper) is an economically and industrially important medicinal plant. However, the characterization of its volatiles has only been analyzed by gas chromatography–mass spectrometry (GC–MS). In the present study, precise characterization of P. longum fruit volatiles has been performed for the first time through advanced two‐dimensional gas chromatography–time‐of‐flight spectrometry (GC×GC–TOFMS). A total of 146 constituents accounting for 93.79% were identified, of which 30 were reported for the first time. All these constituents were classified into alcohols (4.5%), alkanes (8.9%), alkenes (6.71%), esters (6.15%), ketones (0.58%), monoterpene hydrocarbons (1.64%), oxygenated monoterpenes (2.24%), sesquiterpene hydrocarbons (49.61%), oxygenated sesquiterpenes (13.03%), phenylpropanoid (0.23%), and diterpenes (0.2%). Among all the classes, sesquiterpene hydrocarbons were abundant, with germacrene‐D (2.87% ± 0.01%) as the major one, followed by 8‐heptadecene (2.69% ± 0.03%), β‐caryophyllene (2.43% ± 0.03%), n‐heptadecane (2.4% ± 0.04%), n‐pentadecane (2.11% ± 0.05%), and so forth. Further, 20 constituents were observed to be coeluted and separated precisely in the two‐dimensional column. The investigation provides an extensive metabolite profiling of P. longum fruit volatiles, which could be helpful to improve its therapeutic potential.