This study is related to the preparation of biocompatible gold nanoparticles (AuNPs) which are stable in aqueous solutions for a long time. Ultrasmall polyethyleneimine (PEI)-capped AuNPs (PEI-AuNPs) with limited agglomeration were prepared in aqueous solutions at room temperature, which were based on the roles of PEI as a reductant and a stabilizer. PEI-AuNPs with an average size of 8-12 nm formed highly stable nanocolloids with an average hydrodynamic cluster size of around 50 nm in aqueous media. At a low concentration of metal precursor hydrogen tetrachloroaurate OM, the particle size was reduced noticeably. The typical peaks of gold were observed in the X-ray diffraction pattern of AuNPs. The cell viability of 98% was obtained in the case of PEI-AuNPs, while PEI was cytotoxic. The PEI-AuNP is considered to be a potential candidate as a contrast agent for computed tomography.