The chemical composition of rainwaters is important in obtaining information on the aerosols and gaseous species present in the atmosphere. Original data on the concentrations of trace elements and major species in the dissolved and particulate fractions of rainwater samples collected in intertropical Africa were used to determine the potential sources of chemical species. The photographic and mineralogical characterization of rainwater particles using scanning electron microscopy allow to identify the various origins of aerosols and the associated chemical elements: (i) the crustal source characterized by clay minerals, kaolinite (Al, Si), illite (Al, Si and K) and Fe, Ti, and Mn oxides, (ii) vegetation relicts: Mg, Si, Cl, Mn and Zn have been identified in these biogenic particles and (iii) carbonaceous particles (mainly Si) emitted during vegetation fires. Ionic charge balance calculation for the stations located in the rain forest and wet savanna zones (Cameroon, Centrafrican Republic and Ivory Coast) exhibit an anion deficit from 20 to 50 % (between 7 and 9 μeq.l−1). Measured total organic carbon concentrations (between 0.5 and 3.3 mg.l−1), are much higher than acetic and formic acid. The presence of mimic and/or fulvic substances emitted from the vegetation can explain this anion deficit. The results obtained in this study confirm the existence of three important sources of atmospheric compounds in intertropical Africa: (i) the silicate upper crust source: Sc, Ti, Fe, Y, Zr, Nb, Cs, La, Ce, Nd, Yb, Th and U exhibit enrichment factors very close to 1, (ii) the biogenic and biomass burning source characterized by the following elements: Mg, Cl, K, Ca, Mn, Zn, Rb, Sr, and (iii) two minor sources; marine (Mg, Na, Cl) and anthropogenic (Cr, Co, Zn, Ba and Pb). For the stations located in the rain forest zone, all these sources appear strongly linked. High correlations are observed between elements of various origins. This suggest a strong interaction between terrigenous, biogenic, marine and anthropogenic aerosols. The deposition of aerosols onto vegetation and the re-mobilization of the chemical species through natural emissions or biomass burning could explain these correlations and the observed chemical fractionation of marine origin elements such as Cl and Na.