AbstractEsterases are a group of hydrolytic enzymes that split ester bonds by addition of water and are ubiquitously present in diverse biosystems. Although animal esterases are well studied and are catalytically and functionally classified into different groups, plant enzymes have been viewed rather generally and are casually recruited as biochemical markers in morphogenesis, genetic characterization of plants, etc., without functional emphasis. Some volatile oil plants constitutively synthesize their characteristic monoterpene esters, geranyl acetate and linalyl acetate being the most common among them in the acyclic monoterpene class, whereas other plants also synthesize some volatile hemi‐ to sesquiterpene esters but inductively under certain ecological situations, such as herbivory, wounding, etc. This study concerns screening relative distribution of geranyl acetate esterase and linalyl aceate esterase activities in selected medicinal and aromatic plants, and reveals that in plants geranyl acetate (a primary alcohol ester) esterase is commonly present, while linalyl acetate (a tertiary alcohol ester) esterase seems to be highly limited to those plants (e.g. Lippia alba, Mentha citrata) that biosynthesize the tertiary monoterpene alcohol linalool and its ester. Such contrasting distribution of the two discrete types of esterases has been discussed in light of scenario of their microbial counterparts and structure–function relationships established thereon. This study makes it obvious that the GGG(A)‐X motif esterases (acting on tertiary alcohol esters) are rare entities in plants too, similar to microbes. Furthermore, their presence in some volatile oil plants renders such plants novel phytoresources of the GGGX/GGAX motif hydrolases. Detailed characterization of the motif‐specific plant esterases would have an immense impact on understanding of their structure–function relationships in plants. Copyright © 2007 John Wiley & Sons, Ltd.