High-energy (HE) and low-energy (LE) collisionally activated decompositions of octaethylporphyrin (OEP) and its metal complexes (ZnOEP and CuOEP) depend on whether the precursor is produced by electrospray ionization as protonated molecules or by fast atom bombardment as radical cations or protonated molecules. LE activation leads to such simple product-ion spectra that a complete picture of fragmentation emerges only after nine stages of tandem mass spectrometry (MS). HE activation, on the other hand, gives product-ion spectra that afford an integrated view of all the decomposition channels in a single MS/MS experiment. These results are the basis of a recommendation that OEP is an appropriate model compound for investigating energy effects in the collisional activation of organic and bioorganic molecule ions.