Phytochemicals have been isolated from extracts of various Xylopia species (Annonaceae) growing wild in the African rainforest. In contrast, no phytochemical investigations have been reported to date on Xylopia rubescens Oliv. The aim of the present work was to describe the composition of X. rubescens leaf oil. Analysis of the leaf oil has been undertaken by a combination of chromatographic and spectroscopic techniques. Three new compounds have been isolated and their structures elucidated as furanoguaia‐1,4‐diene, furanoguaia‐1,3‐diene and (8Z,11Z,14Z)‐8,11,14‐heptadecatrien‐2‐ol. One other compound is reported for the first time as a natural compound. The oil composition was dominated by both furanoguaiadienes (34.2% and 11.4%, respectively) and by (8Z,11Z,14Z)‐8,11,14‐heptadecatrien‐2‐one (12.8%). The composition of X. rubescens leaf oil varied dramatically from those of the essential oils isolated from other Xylopia species. Copyright © 2013 John Wiley & Sons, Ltd.