The development of an effective, low-cost and natural sorbent is of great significance for phosphorus removal and recovery from small and medium size industrial and municipal wastewater. Commonly used phosphorus removal methods are costly and thus rarely applied in the small-scale WWTPs. This research was aimed at preparing and characterising three different calcium/iron composites for evaluating their sorption performance for the removal of phosphorus from aqueous solutions and domestic wastewater. The obtained composite materials belonging to the Brownmillerite mineralogical subgroup were characterised by the Powder X-ray Diffraction (PXRD), specific surface area analysis by Brunauer-Emmett-Teller (BET) method and scanning electron microscope (SEM). It was found that for aqueous solutions the sorption process is pH- dependent, showing the optimal sorption conditions for phosphorus removal at pH 3 to pH 6. However, all three proposed composites significantly increased the pH of wastewater. All three tested materials adsorbed phosphorus from wastewater. Maximal phosphorus adsorption capacity from the domestic wastewater was 17.75 mg g-1 , 8.25 mg g-1 and 4.46 mg g-1 for CaFeOxide, CaFeHydr and CaFeReg respectively. In further research it is planned to develop an environmentally friendly and cost-effective phosphorus recovery technology with the potential to apply the used sorbent as a slow-release fertiliser in agriculture.