<jats:title>Abstract</jats:title><jats:p>Two new alkaloids, pegamine <jats:italic>β</jats:italic>‐<jats:sc>D</jats:sc>‐glucopyranoside (<jats:bold>1</jats:bold>) and 2‐deoxypeganylacetic acid (<jats:bold>2</jats:bold>), together with the novel 3,4‐dihydro‐4‐hydroxynaphthalene‐2‐carboxylic acid (<jats:bold>3</jats:bold>), were isolated from the aerial part of <jats:italic>Peganum nigellastrum.</jats:italic> The structures of these compounds were elucidated on the basis of spectroscopic analyses, including 1D‐ and 2D‐NMR, and ESI‐MS/MS.