The enhancement effect of 3-mercaptopropionic acid capped gold nanoparticles (NPs) in drug delivery and as biomarkers of drug-resistant cancer cells has been demonstrated through fluorescence microscopy and electrochemical studies. The results of cell viability experiments and confocal fluorescence microscopy studies illustrate that these functionalized Au NPs could play an important role in efficient drug delivery and biomarking of drug-resistant leukemia K562/ADM cells. This could be explored as a novel strategy to inhibit multidrug resistance in targeted tumor cells and as a sensitive method for the early diagnosis of certain cancers. Our observations also indicate that the interaction between the functionalized Au NPs and biologically active molecules on the surface of leukemia cells may contribute the observed enhancement in cellular drug uptake.