Rechargeable batteries are in high demand for future hybrid vehicles and electronic devices markets. Among various kinds of rechargeable batteries, Li-ion batteries are most popular for their obvious advantages of high energy and power density, ability to offer higher operating voltage, absence of memory effect, operation over a wider temperature range and showing a low self-discharge rate. Researchers have shown great deal of interest in developing new, improved electrode materials for Li-ion batteries leading to higher specific capacity, longer cycle life and extra safety. In the present study, we have shown that an anode prepared from interface-controlled multiwall carbon nanotubes (MWCNT), directly grown on copper current collectors, may be the best suitable anode for a Li-ion battery. The newly developed anode structure has shown very high specific capacity (almost 2.5 times as that of graphite), excellent rate capability, nil capacity degradation in long-cycle operation and introduced a higher level of safety by avoiding organic binders. Enhanced properties of the anode were well supported by the structural characterization and can be related to very high Li-ion intercalation on the walls of CNTs, as observed in HRTEM. This newly developed CNT-based anode structure is expected to offer appreciable advancement in performance of future Li-ion batteries.