An upflow anaerobic sludge blanket (UASB) reactor was used to investigate the effect of adding Fenton sludge (FS) on the anaerobic digestion of actual papermaking wastewater. The results showed that a one-time addition of 10 g/L FS could sustainably promote the performance of UASB for more than 40 days. The organic matter removal efficiency increased by 15.56%, and the biogas production increased by 24.52%. The proportion of methane in biogas increased by 12.87%. Adding FS increased the capacitance values of sludge extracellular polymeric substances and the electron transfer system activity in reactor increased by 1.76 times. The dehydrogenase activity and coenzyme F420 of the sludge increased by 1.54 and 2.11 times, respectively. Adding FS enriched the iron-reducing bacteria (Thermodesulfobacteriota) and hydrolytic acid-producing bacteria (Chloroflexota and Synergistota), thereby promoting the hydrolysis and acidification process. Adding FS was beneficial to the enrichment of methanogen, especially Methanosaeta, significantly increasing the methane production.