The interaction between HAuCl4 and DNA has enabled creation of DNA-templated gold nanoparticles without formation of large nanoparticles. It was found that spheral DNA-HAuCl4 hybrid of 8.7 nm in diameter, flower-like DNA-HAuCl4 hybrid, nanoparticles chains and nanoparticles network of DNA-HAuCl4 hybrid could be obtained by varying the reaction conditions, including DNA concentration and reaction temperature. The intermediate product was investigated by shortening the reaction time of DNA and HAuCl4, and the obtained nanoparticles preserved a small DNA segment, which indicated that the reaction between DNA and HAuCl4 had a process. The addition of reduction reagent resulted in DNA-templated gold nanoparticles and nanoflowers, respectively. UV-vis absorption spectra were used to characterize the DNA-HAuCl4 hybrid and the gold nanostructures templated on DNA, and XPS spectra were used to compare the composition of DNA-Au(III) complex and gold nanoparticles. AFM and TEM results revealed that the spheral gold nanoparticles of about 11 nm in size and flower-like gold nanoparticles were formed after the addition of NaBH4.