This article analyses the as-cast state of practically unknown Fe-P-based cast alloys with or without an addition of carbon and/or boron, cast into a grey cast iron mould. The melting intervals of the alloys were determined by DSC analysis, and the microstructure was characterized by optical and scanning electron microscopy with an EDXS detector. The hardness and microhardness of the alloys were also measured. Their hardness reached values between 52 and 65 HRC depending on chemical composition and microstructure, showing their high abrasion resistance. The high hardness is a consequence of the eutectic and primary intermetallic phases of Fe3P, Fe3C, Fe2B or mixed type. By increasing the concentration of metalloids and combining them, the hardness and brittleness of the alloys were increased. The alloys with predominantly eutectic microstructures were the least brittle. Depending on the chemical composition, the solidus and liquidus temperatures ranged from 954 °C to 1220 °C and were lower than those of the well-known wear-resistant white cast irons.