Azomethine ylides derived in situ from l-proline and aryl aldehydes underwent regioselective and stereoselective cycloadditions with diaryl cycloahexanone to form a series of spiro-pyrrolizidine compounds. By using equimolar proportions of the reactants in DMF, only a single mono-adduct, namely 6'-arylidene-1-aryl-3-aryl-spiro[pyrrolizidine-2,2'-cyclohexanone], was formed, the second double bond in the dipolarophile remaining unaffected. Structure elucidation was achieved by detailed spectroscopic analyses and XRD studies. Interesting solid-state structural characteristics were revealed by XRD analysis. © 2014 HeteroCorporation.