The possibility of using vanadyl ions as paramagnetic biomarkers for the identification of traces of primitive life fossilized in silica rocks is studied by cw-EPR, ENDOR, HYSCORE, and DFT calculations. It is well-known that porphyrins, which are common to all living organisms, form vanadyl-porphyrin complexes in sediments deposited in oceans. However, the stability of these complexes over a very long time (more than 3 billion years) is not known. By encapsulating vanadyl-porphyrin complexes in silica synthesized by a sol-gel method to mimic SiO(2) sediments, we studied the structure and stability of these complexes upon step heating treatments by monitoring the evolution of the g factor and of the hyperfine interactions with (51)V, (1)H, (14)N, (13)C, and (29)Si nuclei. It is found that vanadyl-porphyrin complexes are progressively transformed into oxygenated vanadyl complexes by transfer of the VO(2+) ion from the porphyrin ring to the mineral matrix. The organic component is transformed into carbonaceous matter which contains paramagnetic centers (IOM(*) centers). To test the validity of this approach, we studied by EPR a 3490 million years old chert (polycrystalline SiO(2) rock) containing some of the oldest putative traces of life. This rock contains oxygenated vanadyl complexes and IOM(*) centers very similar to those found in the synthetic analogues.