The influence of gold particle addition on structural and magnetic ordering of iron oxide in a glass matrix was studied. The silica–phosphate glasses containing iron oxide and Au were prepared by the melt quench technique. Evolution of crystalline phases was studied by X-ray diffraction (XRD). Magnetic properties were investigated by means of a Superconducting Quantum Interference Device (SQUID) magnetometer and room temperature Mössbauer spectroscopy. The microstructure exhibited the formation of 30–40 nm size particles. The samples showed the formation of magnetite and hematite as major crystalline phases. Magnetic studies revealed the relaxation of magnetic particles. Blocking temperature of investigated sample increased with an increase of Au content implying an increase in the strength of magnetic interactions. Mössbauer spectroscopy has shown the presence of both doublets and magnetic sextets. The magnetization value increased as Au content was increased, which is attributed to the increase in magnetic and structural ordering.