Purpose Phosphorus (P) is often the main limiting factor for plant growth in highly weathered tropical soils. Phosphate use efficiency and crop yields could be increased in low-input agroecosystems through cropping systems that favor organic matter accumulation or regular additions of composts and manure. Our objective was to determine the amounts and forms of P according to companion crops (Brachiaria ruziziensis-a grass species-or Cajanus cajan-a leguminous species) and tillage systems (conventional or no-tillage). Materials and methods Soil P pools were determined (P-resin, P-Olsen, PNaOH-EDTA, and P-total) and P species were characterized by P-31 NMR spectroscopy. Results and discussion The concentrations of available and labile inorganic P (P-resin, Pi(Olsen), and Pi(NaOH-EDTA)) were greater in soil samples where companion crops (Brachiaria ruziziensis or Cajanus cajan) and maize were planted on the same row, with a more significant effect with the legume species. According to the P-31 NMR, it is mostly the proportion and amount of P-Orthophosphate that was increased, with a slight increase of the content of P-Monoester. Overall, there was a decrease of the proportion of organic P (Po-NMR/P-NMR) from 32 to 16% when the legume companion crop was associated with maize. Conclusions The tillage systems did not lead to any change in the amounts and forms of P. Companion crops are thought to increase available P through mineralization of Po from plant residues and soil organic matter, leading to an increase of fluxes between active P pools.