Ag/AgCl-based structures have recently been receiving considerable attention as visible-light-driven plasmonic photocatalysts, wherein the fabrication of Ag/AgCl species shaped with an anisotropic morphology is considered to be an efficient way to enhance their performances. While the past decade has witnessed great progress in this direction, it is still strongly desired to initiate a green and low-cost protocol for the synthesis of Ag/AgCl based structures with high catalytic activity. Using a surfactant-assisted synthesis protocol, wherein a cationic bola-type surfactant of chloride counteranions serves both as a reactant (namely, source of chlorine) for the generation of AgCl structures and as a directing template to assist the formation of anisotropic structures, we herein report that cube-like Ag/AgCl with blunt edges could be fabricated simply by dropping an aqueous solution of silver nitrate into an ethanol solution of the hexane-1,6-bis(trimethylammonium chloride) surfactant. Importantly, compared to the sphere-like counterparts manufactured using a conventional tadpole surfactant, the as-fabricated cube-like structures exhibit substantially improved catalytic performances under visible-light or natural-sunlight irradiation. It has been revealed that photogenerated holes might serve as the main active species during the catalytic process. Meanwhile, our results have disclosed that in contrast to the sphere-like Ag/AgCl structures, the as-constructed cube-like structures are relatively enriched with high-index AgCl facets of smaller hole effective mass, which promote a faster carrier transfer, facilitate the migration of the photogenerated holes to the surface to be involved in photocatalytic reactions, and suppress carrier recombination, leading to their enhanced photocatalytic performances. Considering the tremendous diversity of surfactants (bola-, gemini-, polymeric surfactants etc.) with various halide counteranions and their sophisticated template effects, our new strategy might open up new opportunities for silver/silver halide (Ag/AgX, X = Cl, Br, and I)-based plasmonic structures with various morphologies and with superior light-to-chemical energy conversion capability.