Herein, we introduce a tailored mussel-inspired concept to facilitate the sustainable immobilization of silver nanoparticles (Ag NPs), which are accepted for the effectiveness in controlling the silver nanoparticle density and morphology onto the surface of the graphene oxide sheets (GO). Immobilization of Ag NPs on polydopamine (PDOP) functionalized GO is performed via the self-polymerization of dopamine by a facile in situ reduction method. The catalytic ability of the as-synthesized Ag@PDOP-rGO catalyst was searched for the reduction of 4nitrophenol (4-NP) to 4-aminophenol (4-AP) as a class of widespread toxic organic pollutant. The dopamine mediated graphene hybrid with Ag NPs exhibited excellent catalytic reduction activities due to promoting the electron transfer and the dispersion of small-sized silver nanoparticles imposed upon the surface of graphene. The resulting hybrid exhibited 15 times higher catalytic activity than that of the graphene/silver hybrid without any modification.