This work reports on the outcome of the calcination of gold nanoparticles incorporated polyacrylonitrile nanofibers in air which results in the formation of gold spherical and flake cluster assemblies. The architecture and morphology of gold nanostructures play a role in determining their different applications. The results of this research showed that calcination at 650 degrees C for 5 h led to almost complete disintegration and disappearance of the poly(acrylonitrile) matrix and polyhedral nanostructures were formed. FTIR analysis showed the complete disappearance of poly(acrylonitrile) matrix at calcination temperatures of 850 degrees C and 1000 degrees C. XRD analysis also showed the complete disappearance of poly(acrylonitrile) at calcination temperatures above 850 degrees C. SEM micrographs taken after calcination of the precursor showed that calcination around 850 degrees C leads to the formation of spherical gold clusters, whereas, calcination at 1000 degrees C produces gold flake clusters.