The polyethylene glycol (PEG) modified gold nanoparticle complex was synthesized by a one-solution synchrotron x-ray irradiation method. The impact on the structure and morphology of the gold nanoparticles of process parameters such as the PEG molecular weight, the PEG/gold molar ratio and the x-ray dosage were investigated. The size of PEG modified gold particles was found to decrease with increasing PEG addition and x-ray dosage. With the capability to monitor the absorption spectra in situ during the fast synthesis process, this opens the way to accurate control of the size and distribution. PEG chains with an intermediate length (MW6000) were found optimal for size control and colloidal stability in biologically relevant media. Our x-ray synthesized PEG-gold nanoparticles could find interesting applications in nanoparticle-enhanced x-ray tumour imaging and therapy.