Most, if not all, extant cycads are pollinated by insects which use the cones as larval brood sites. These interactions appear to be mediated by cone volatiles, and, in some species, by patterns of thermogenesis. We investigated the chemical composition of volatile emissions and patterns of thermogenesis in cones of the South African cycad Encephalartos natalensis, using a gas chromatograph–mass spectrometer (GC–MS) and miniature temperature data loggers (ibuttons), respectively. This was done during various developmental stages (before and during receptivity and pollen release) for both female and male cones. A total of 31 compounds were identified in headspace samples; 17 of which were common to both sexes, 12 found only in male cones, and two found only in female cones. The major volatiles in pollen and female cones are (3E)-1,3-octadiene (averaging 54.25% and 15.82% of total emissions), (3E,5Z)-1,3,5-octatriene (averaging 13.37% and 47.66%), and α-pinene (averaging 16.29% and 12.24%). Female cones were not thermogenic before and during receptivity whereas pollen cones were thermogenic during pollen shedding. Thermogenesis of male cones occurred between 1400h and 1530h on successive afternoons, reaching an average of c. 10.5°C above ambient temperature. Volatile emissions and thermogenesis occurred in association with insect activity on the cones suggesting that they both play a role in regulating insect behaviour.