Fluorescent brighteners (FBs) are a group of mass-produced dyestuff chemicals that have been extensively used for decades. However, knowledge of their occurrence in municipal wastewater treatment plants on a large geographical scale remains unknown. Herein, we implemented the first nationwide survey for wastewater-derived FBs in sludge across major cities in China. All 25 target FBs were detected in the nationwide sludge. Ionic FBs exhibited much higher concentrations than nonionic FBs. The total sludge concentrations of 25 FBs (∑ 25 FBs) ranged from 7300 to 1,520,000 ng/g, with a median of 35,300 ng/g. A clear geographical distribution of significantly higher concentrations of FBs was found in East and Central China than in West China ( p < 0.05). The sludge concentrations of ∑ 25 FBs were correlated well with the gross domestic product (GDP) and population size at the provincial level in China ( p < 0.05), demonstrating the significance of anthropogenic impacts on FB levels in urban sludge. The nationwide annual emission of total FBs into sludge in China is estimated to be 835 tons/year, of which 134 tons/year is directly released into sludge-applied soils. Our work highlights another new class of chemicals that significantly contribute to the chemical mixtures in urban sludge and thus require immediate attention.