<jats:title>Abstract</jats:title><jats:p>The methanolic extract of dried ground seeds of <jats:italic>Piper nigrum</jats:italic> L<jats:sc>inn</jats:sc>. afforded fourteen compounds, of which thirteen were amides, including two new isomeric insecticidal amides, pipsaeedine (<jats:bold>1</jats:bold>) and pipbinine (<jats:bold>2</jats:bold>), along with eleven known amides and piptaline; (this is the first report of isolation of these compounds from this plant). The structures of <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> have been elucidated as (<jats:italic>E</jats:italic>,<jats:italic>E</jats:italic>)‐1‐[(<jats:italic>E</jats:italic>)‐5‐(7‐{6‐[5‐(piperidin‐1‐yl)‐5‐oxopent‐3‐enyl]‐1,3‐benzodioxol‐4‐yl}‐1,3‐benzodioxol‐5‐yl)‐1‐oxopenta‐2,4‐dienyl]piperidine and (<jats:italic>E</jats:italic>,<jats:italic>E</jats:italic>)‐1‐[(<jats:italic>E</jats:italic>)‐5‐(4‐{6‐[5(piperidin‐1‐yl)‐5‐oxopent‐3‐enyl]‐1,3‐benzodioxol‐4‐yl}‐1,3‐benzodioxol‐5‐yl)‐1‐oxopenta‐2,4‐dienyl]piperidine, respectively, through extensive 1D‐ and 2D‐NMR spectral studies, while the known constituents have been identified through comparison of their spectral data with those reported in the literature. Compounds <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> exhibited toxicities of 45.0 and 40.0 ppm, respectively, against fourth instar larvae of <jats:italic>Aedes aegypti</jats:italic> Liston.