In this report, a simple and effective low-temperature synthesis route has been proposed to smoothly achieve monodisperse tin nanoparticles upon monolithic 3D nanoporous copper (3D-NPC@MTNPs) from chemical dealloying of as-cast Al-45 at% Cu alloy sheets in HCl solution; they exhibit superior Li storage properties and ultralong cycle life as the anode for lithium ion batteries (LIBs). The results show that the 3D-NPC@MTNPs composite can be fabricated on a large scale by electroless plating of Sn on a uniform NPC matrix with a pore size of ca. 200 nm in an acidic plating bath below room temperature. Compared to two dimensional copper foil supported tin thin films (2D-CF@TTFs), the 3D-NPC@MTNPs electrode displays a markedly higher first reversible capacity of 0.485 mA h cm-2 as well as superior cycling stability with 52.4% capacity retention and over 96.7% coulombic efficiency after 500 cycles. This can be largely ascribed to the synergistic effect between the favorable monodispersity of Sn nanoparticles with ultrafine particle size and single crystal nature and the unique 3D nanoporous electrode architecture with a large specific surface area and a good mass transfer channel, which facilitates the accommodation of mechanical strain, improvement of structural stability, enhancement of bonding force, and acceleration of mass transfer, which are indicative of a quite promising candidate as a high-performance anode for LIBs.