Fragmentation pathways of nine synthetic organophosphorus compounds, belonging to the following types spiro(indene‐2,3′‐pyrazole)‐ phosphanylidene, spiro(indene‐2,3′‐pyrazole)phos‐ phonates, spiro(1,2,4‐diazaphosphole‐3,2′‐indenes), and (1,3‐dioxo‐1,3‐dihydro‐2H‐isoindol‐2‐yl) phosphonates, were investigated by electron impact mass spectrometry with the aim of obtaining a better understanding of their fragmentation processes. The intensity of recorded molecular ion peaks showed various values depending on the nature of compounds. Characteristic fragment ions were formed by successive loss of simple side functional groups followed by decomposition of indenyl‐1,3‐dione and isoindole‐1,3‐dione moieties connected with terminal groups or heterocycles. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:254–264, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.21011