The article addresses the role of surfactant headgroup structure on hybrid surfactant performance for water-in-CO2 (w/c) microemulsion stabilization. The synthetic procedure, aqueous properties, and phase behaviour of a new hybrid sulfoglutarate surfactant are described. The sulfoglutarate version has an extra methylene group incorporated into the hydrophilic headgroup. The related hydrocarbon (AOT14 and AOT14GLU) and fluorocarbon (di-CF2 and di-CF2GLU) surfactants were used to form w/c microemulsions. For these two groups, the aqueous properties and w/c phase stability of both sulfoglutarates and sulfosuccinates were found to be similar. The newly synthesized hybrid CF2/AOT14GLU (sodium (4H,4H,5H,5H,5H-pentafluoropentyl-2,2-dimethyl-1-propyl)-2-sulfoglutarate) proved to be more efficient than the normal sulfosuccinate, hybrid CF2/AOT14 in terms of the aqueous behaviour and w/c phase stability. Hybrid CF2/AOT14GLU more effectively decreased the air-water surface tension by similar to 2 mN m(-1) and lowering the cloud pressures on CO2 by similar to 150 bar. (C) 2016 Published by Elsevier B.V.