The recycle and light-harvesting of powder photocatalysts in suspended system are bottlenecks for practical applications in photocatalysis. Herein, we demonstrate the facile synthesis of self-floating amphiphilic black TiO2 foams with 3D macro-mesoporous architectures through freeze-drying method combined with cast molding technology and subsequent high-temperature surface hydrogenation. Ethylenediamine plays bifunctional roles on acid-base equilibrium and "concrete effect" on stabilizing the 3D macro-mesoporous networks against collapsing, which also inhibit the phase transformation from anatase-to-rutile and undesirable grain growth during hydrogenation at 600 degrees C. The resultant black TiO2 foams, which can float on the water, extend the photoresponse from UV to visible-light region and exhibit excellent solar-driven photocatalytic activity and long-term stability for complete mineralization of floating insoluble hexadecane and some typical pesticides. Especially for floating contaminant hexadecane, the photocatalytic reaction apparent rate constant k is similar to 7 times higher than that of commercial Degussa P25 under AM 1.5 irradiation. This enhancement is attributed to the 3D macro-mesoporous networks facilitating mass transport, the super amphiphilicity benefiting rapid adsorption, the floating feature and Ti3+ in frameworks favoring light-harvesting and spatial separation of photogenerated electron-hole pairs. The novel self-floating photocatalyst will have real practical applications for mineralizing floating contaminants in natural environment. (C) 2017 Elsevier B.V. All rights reserved.