The first reported synthesis and characterisation of phosphaethynolate came from Becker et al. in 1992. They were able to isolate the anion as a lithium salt (in 87% yield) by reacting lithium bis(trimethylsilyl)phosphide with dimethyl carbonate . The x-ray crystallographic analysis of the anion determined the  bond length to be  (indicative of a phosphorus-carbon triple bond) and the  bond length to be . Similar studies were performed on derivatives of this structure and the results indicated that dimerisation to form a four-membered Li ring is favoured by this molecule.
Ten years later, in 2002, Westerhausen et al. published the use of Becker's method to make a family of alkaline earth metal salts of PCO ; this work involved the synthesis of the magnesium, calcium, strontium and barium bis-phosphaethynolates. Like the salts previously reported by Becker, the alkali-earth metal analogues were unstable to moisture and air and thus were required to be stored at low temperatures (around ) in dimethoxyethane solutions.
It was not until 2011 that the first stable salt of the phosphaethynolate anion was reported by Grutzmacher and co-workers . They managed to isolate the compound as a brown solid in 28% yield. The structure of the stable sodium salt, formed by carbonylation of sodium phosphide, contains bridging PCO units in contrast to the terminal anions found in the previously reported structures. The authors noted that this sodium salt could be handled in air as well as water without major decomposition; this emphasises the significance of the accompanying counter cation in stabilisation of PCO.
Direct carbonylation was a method also employed by Goicoechea in 2013 in order to synthesis a phosphaethynolate anion stabilised by a potassium cation sequestered in 18-crown-6 . This method required the carbonylation of solutions of  at  and produced by-products that were readily separated during aqueous work ups. The use of aqueous work ups reflects the high stability of the salt in water. This method afforded the PCO anion in reasonable yields around 43%. Characterisation of the compound involved infra-red spectroscopy; the band indicative of the  triple bond stretch was observed at .