Various carbon materials have been extensively used as anode materials for rechargeable Li-ion batteries because of their consistent performance and potentialities. MWCNTs have also attracted attention as anode materials because of their high conductivity, high aspect ratio, good tensile strength etc. which makes them suitable for fabricating free standing anode. Multiwalled carbon nanotubes (MWCNTs) of length 100-150 nm prepared by Chemical Vapor Deposition is used to make free standing paper by simple vacuum filtration technique. The free standing paper when used as anode for Li ion battery shows a discharge capacity (rate C/10) of 181 mAh/g in the first cycle which increases to 197 mAh/g after the 50th cycle. SnO₂/long length MWCNTs nanocomposite is also prepared by chemical route. Free standing anode made from the nanocomposite shows a very high capacity 330 mAh/g in the first cycle which increases upto 383 mAh/g in the 50th cycle. Various characterization techniques like SEM, TEM, TGA, XRD and Raman spectroscopy have been carried out to evaluate the structure of the anode that is further correlated to its performance in Li-ion cell. This peculiar behavior of increase in capacity as cycling progresses is very remarkable and is promising for batteries.