We have reported the synthesis of dimethylformamide (DMF)-protected gold nanoclusters using a surfactant-free DMF reduction method. DMF-protected gold nanoclusters (Au NCs) are obtained without the formation or gold nanoparticles and bulk metals as byproducts using a hot injection process for the homogeneous reduction. The as-prepared DMF-protected Au NCs were a mixture of various-sized Au NCs with a cluster number of less than 20 including at least Au-8 and Au-13. The photoluminescence emission from Au-8 and Au-13 was confirmed in the photoluminescence spectra. The Au NCs are stabilized with DMF molecules through the interaction of amide groups of DMF with Au NCs, DMF-protected Au NCs in solution were found to have high thermal stability, high dispersion stability in various solvents, and high photochemical stability. The DMF-protected Au NCs dispersed well for at least a month in various solvents such its water, acid (pH 2), alkali (pH 12) and 0.5 M NaCl aqueous solution, and methanol without further surface modification. The thermal stability of ME-protected Au NCs was similar to 150 degrees C, which was comparable to that of thiolate-protected Au NCs. The photobleaching of Au NCs in water gradually occurred under UV light irradiation (356 nm, 1.3 mW/cm(2)) because of the photoinduced oxidation of Au NCs. After 8 h irradiation, the fluorescence intensity slowly decreased to similar to 50% of the maximum and to similar to 20% after 96 h under the present condition. compared to the photobleaching of CdSe semiconductor quantum dots. We also found that the fluorescence intensity remained to be about 30% of the maximum even in the presence of concentrated 30% H2O2. These findings demonstrate that the photobleaching process under the UV irradiation is effectively suppressed for DMF-protected Au NCs.