The chemical volatile profiles of four plant species from Benin were established via SDE/GC–MS and SPME/GC–MS, and were compared to chemical profiles obtained by hydrodistillation/GC–MS. Essential oils and selected identified compounds were used to perform fumigant tests and contact “no choice” tests against adults of the red flour beetle Tribolium castaneum, an important pest insect in stored products worldwide. The chemical profiles and the concentrations of the main compounds varied with the method used. Geranial (hydrodistillation, SPME) and geraniol (SDE) for Cymbopogon citratus, piperitone for Cymbopogon schoenanthus (hydrodistillation, SPME, SDE), E-p-mentha-1(7), 8-dien-2-ol for Cymbopogon giganteus (hydrodistillation, SPME, SDE), neo-isopulegol (SDE) and citronellal (hydrodistillation and SPME) for Eucalyptus citriodora, were identified as main volatile compounds. By fumigation, the LC50 values obtained after 24h for essential oils of C. citratus, C. giganteus, C. schoenanthus, E. citriodora, and for piperitone and citronellal were 4.2mL/L air, 2.3mL/L air, 2.1mL/L air, 2.0mL/L air, 0.5mL/L air and 1.2mL/L air, respectively. Furthermore, mortalities of 100%, 82%, 75%, 72%, 68% and 42%, respectively, were found for piperitone at 2.4mL/L air, citronellal at 2.1mL/L air, and essential oil extracted from E. citriodora, C. schoenanthus, C. giganteus and C. citratus, at 4mL/L air. By contact “no choice” test, the LC50 values for the crude oils after 72h were: 15% (w/v), 6% (w/v), 6% (w/v) and 5% (w/v) for C. citratus, C. giganteus, C. schoenanthus and E. citriodora, respectively. After 72hours, mortalities of 18%, 67%, 73%, 82%, 87% and 40% for essentials oils (8% w/v) of C. citratus, C. giganteus, C. schoenanthus, E. citriodora, piperitone at 4.7% w/v, and citronellal at 4.2% w/v, respectively, were obtained. The essential oil from C. schoenanthus and E. citriodora as well as piperitone and citronellal represent potential valuable alternative pesticides to conquer the resistance of T. castaneum to synthetic insecticides.