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A group of not well known anionic phosphorus‐containing surfactants have been obtained. In these surfactants the hydrophobic chain is directly linked to the phosphorus atom through a P‐C bond. These products are alkylphosphinates with C10, C12, C14 and C16 alkylic chains. The products have been prepared by direct reaction between sodium hydrophosphite and the corresponding α‐olefin, using tert‐butyl perbenzoate as reaction initiator. Surfactants properties such as surface tension, foaming power and wetting power of the sodium and ammonium salts of all these alkylphosphinates have been measured.