The cetane number (CN), being related to ignition and combustion behavior, is a prime indicator of the quality of diesel fuels, including those derived from renewable resources such as biodiesel. While many effects of compound structure are known or have been postulated, experimental data have not always been available for the various ester components of biodiesel and a comprehensive evaluation including some structural features not yet experimentally investigated such as double bond configuration and position is lacking. In this work, existing CN data of fatty esters are complemented by studying C18 esters with differing double bond positions and double bond configurations. For the first time, CNs, determined as derived cetane number (DCNs), of neat trans fatty acid methyl esters, methyl elaidate (methyl 9(E)octadecenoate) and methyl linolelaidate (methyl 9(E), 12(E)-octadecenoate), were determined as were the CNs of the C18: 1 positional isomers methyl petroselinate (methyl 6(Z)-octadecenoate) and methyl asclepate (methyl 11(Z)-octadecenoate). The CNs of the positional and geometric isomers of methyl oleate are close to the CN of methyl oleate. These data are compared to other previously determined CN data. Furthermore, the applicability of CN data is evaluated using an extensive collection of CN determinations for methyl oleate as "standard'' fatty acid (methyl) ester. The average CN value for methyl oleate is in the range of 56-58 with a CN of 57 suggested for calculating purposes. Similarly, uncertainty ranges could be established for CNs of other fatty materials. The data are also useful for predicting CNs of compounds for which CNs are not readily available or easily determinable. Published by Elsevier Ltd.