<jats:title>Summary</jats:title><jats:p>Cation‐ and <jats:italic>S</jats:italic>‐adenosyl‐<jats:sc>l</jats:sc>‐methionine (AdoMet)‐dependent plant natural product methyltransferases are referred to as CCoAOMTs because of their preferred substrate, caffeoyl coenzyme A (CCoA). The enzymes are encoded by a small family of genes, some of which with a proven role in lignin monomer biosynthesis. In <jats:italic>Arabidopsis thaliana</jats:italic> individual members of this gene family are temporally and spatially regulated. The gene <jats:italic>At1g67990</jats:italic> is specifically expressed in flower buds, and is not detected in any other organ, such as roots, leaves or stems. Several lines of evidence indicate that the <jats:italic>At1g67990</jats:italic> transcript is located in the flower buds, whereas the corresponding CCoAOMT‐like protein, termed AtTSM1, is located exclusively in the tapetum of developing stamen. Flowers of <jats:italic>At1g67990</jats:italic> RNAi‐suppressed plants are characterized by a distinct flower chemotype with severely reduced levels of the <jats:italic>N</jats:italic> ′,<jats:italic>N</jats:italic> ′′<jats:italic>‐</jats:italic>bis‐(5‐hydroxyferuloyl)‐<jats:italic>N</jats:italic> ′′′‐sinapoylspermidine compensated for by <jats:italic>N<jats:sup>1</jats:sup></jats:italic>,<jats:italic>N<jats:sup>5</jats:sup></jats:italic>,<jats:italic>N<jats:sup>10</jats:sup></jats:italic>‐tris‐(5‐hydroxyferuloyl)spermidine derivative, which is characterized by the lack of a single methyl group in the sinapoyl moiety. This severe change is consistent with the observed product profile of AtTSM1 for aromatic phenylpropanoids. Heterologous expression of the recombinant protein shows the highest activity towards a series of caffeic acid esters, but 5‐hydroxyferuloyl spermidine conjugates are also accepted substrates. The <jats:italic>in vitro</jats:italic> substrate specificity and the <jats:italic>in vivo</jats:italic> RNAi‐mediated suppression data of the corresponding gene suggest a role of this cation‐dependent CCoAOMT‐like protein in the stamen/pollen development of <jats:italic>A. thaliana</jats:italic>.