The increased production of electrical and electronic waste (E-waste) has resulted in a greater Au presence in E-waste than in ores. As such, it is imperative to selectively recover Au from the wastewater of E-waste. In this work, a designed self-assembled thiourea-crosslinked reduced graphene oxide framework (TU-rGOF) balls for fixed-bed reactors was successfully synthesized via a facile crosslinking reaction between thiourea (TU) and graphene oxide (GO), in which TU simultaneously transforms GO into reduced graphene oxide (rGO) during the heating process. This material exhibits excellent adsorption performance and reduced Au(III) into Au0 in aqueous solution. The adsorption efficiency reaches 95 % between pH 1 and 3. Most importantly, the TU-rGOF ball demonstrated high selectivity toward Au(III) among coexisting metal ions, including Cu(II), Pb(II), Zn(II), and Ni(II). 99 % of Au(III) at a low concentration (1 or 10 mg/L Au(III)) in a highly acidic solution (pH 2.0) was removed, yielding a maximum Langmuir adsorption capacity of 97.09 mg g−1 (TU-rGOF ball) and 833.3 mg g−1 (TU-rGO only). The best adsorption fitting to the Langmuir model also suggests monolayer coverage of Au on the TU-rGOF ball surface. Based on scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses, Au(III) adsorption by TU-rGOF ball was proposed to be governed by chelation and redox. Furthermore, TU-rGOF balls also exhibited excellent selective adsorption performance (∼90 % Au adsorption at an Au concentration ∼ 1 mg/L) in real E-waste wastewater (pH = 0.07) containing significant amounts of competitive ions. This study provides novel implications for applying TU-rGOF balls to fixed-bed reactors for low-concentration Au(III) recovery from complex recycled E-waste solutions.