Biobased surfactants were synthesized using poly(glycerol-succinate) as the polar head group and variable acyl groups as hydrophobic tails. Acyl chain lengths ranged from 8 to 14 carbon atoms. The resulting oligomeric surfactants were characterized by quantitative 13C nuclear magnetic resonance (NMR), acid values and size exclusion chromatography. Investigation of the physicochemical properties of the acyl poly(glycerol-succinate) surfactants revealed their potential for use in a wide array of applications. The acyl poly(glycerol-succinate) functional properties appeared to be particularly concentration-dependent. This study highlights the relative impact of acyl chain length on the polymeric structure, physicochemical and functional behaviors, and biodegradability of the acyl poly(glycerol-succinate) surfactants.