A novel method has been developed for the preparation of highly active and thermally stable Au nanocatalysts, including a ZrO2-TiO2 (hereafter referred to as ZT) mixed oxide layer, a moveable Hollow Fe3O4 (hereafter referred to as HwFe3O4) magnetic core and some Au NPs of 5–8 nm. This method involves the in situ reduction of Au NPs on the C/HwFe3O4 nanospheres by using the C layer as the reducing agents. SEM, TEM, EDX, and XRD were employed to characterize the prepared samples. The results showed the ZT layer could increase the thermal stability and reactivity. The reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) was employed as a model reaction to test catalytic performance in this work. The results showed the ZT/Au/C/HwFe3O4 nanospheres calcined at 750 °C showed the highest catalytic activity, compared to the samples calcined at 550 °C and RT, respectively. Meanwhile, the sample (750 °C) still has certain of magnetism, suggesting the desired samples could be separated by magnet. Finally, the catalyst was reused for several cycles to reduce the nitrophenol.