Laser Raman microspectroscopy was used as a microchemical analysis technique to characterize the wall chemistry of organic-walled microfossils (acritarchs and prasinophytes) extracted from Proterozoic (Tonian: ca. 900 Myr) and early Palaeozoic (Silurian: ca. 420 Myr) marine sediments in the Volta Basin of Ghana, and the Ghadamis Basin of Libya, respectively. Raman spectra of Proterozoic acritarchs show spectral features characteristic of kerogenous compounds at ~1350 and ~1600 cm−1, consistently with previously published reports. In addition, spectra from prasinophyte algae from the Silurian sample also show an interesting spectral feature at ~1707 cm−1 indicative of carbonyl moieties.Broadly speaking, shape and position of Raman bands appear to depend on the nature of the specimen considered, suggesting that laser micro-Raman analysis can potentially be used to establish phylogenetic relationships (high-rank taxonomy) among the main groups of pre-Cambrian to Palaeozoic palynomorphs.