In order to develop a new natural tobacco flavor, the concrete of peels of Citrus grandis ( L.) Osbeck was made by accelerative solvent extraction (ASE) under the pressure of 10.34 MPa at 100°, and the volatile constituents in the concrete were analyzed by gas chromatography-mass spectrometry (GC/MS). The concrete was pyrolyzed in helium atmosphere at 300, 450, 600, 750, and 900° separately, and pyrolyzates were analyzed by on-line pyrolysis-GC/MS, and the concrete was evaluated as a cigarettes flavoring. The results showed that: 1) 53 volatile constituents were identified in the concrete, and most of them were terpenoids, alcohols and esters; 2) 23, 30, 35, 50, and 55 volatile constituents were identified in the pyrolyzates at 300, 450, 600, 750 and 900°, respectively; 3) the most constituents in the concrete were not detectable in the pyrolyzates at 300°, only part of furfural, cis-linalool oxide, trans-linalool oxide, carvone and palmitic acid remained until the temperature reached 600°. At 600°, the pyrolyzates were mainly aldehydes, ketones, esters and funans; benzene and PAHs emerged and their contents increased with the rise of temperature. Above 600°, the major components were benzene and PAHs; 4) the concrete improves and modifies the smoking taste of cigarette, enhances smoke flavor, and reduces irritation.