To address the instability and repulsive interaction of carbon nanotubes (CNTs) in Li-ion batteries, mixed polymers (polyacrylonitrile and polyvinylpyrrolidone) were employed as matrix support to ensure that CNT particles remain in place during charge/discharge process and prevent particle migration. Various CNT-based anodes have been reported, but these require metal support that could result in contact resistance. Hence, free-standing CNT electrodes are an attractive option. A simple method of electrospinning polymers and calcination at 800 °C is presented with CNT loading as high as 50 wt % can be obtained without binder and acts as main active material rather than an additive as described in previous studies. The anode [pyrolyzed polymer (PP)-CNT] showed excellent performance with a high discharge specific capacity of 960 mA h/g at a current density of 200 mA/g. The capacity at a higher current density (1600 mA/g) remained greater than graphite (372 mA h/g) at 521 mA h/g and showed a high stability for 675 cycles without exhibiting any significant capacity loss with a Coulombic efficiency of >95%. A rate capability experiment showed the reversibility of PP-CNTs after subjecting them to an increasing current density and regaining >95% of the initial capacity at a low current density (200 mA/g). The high capacitive performance of the material is attributed to the high loading of CNTs and their containment within the bulk of the polymer matrix to prevent particle migration and agglomeration as well as the capacity of the nanofibers to preserve a tight proximity of the electrolyte-electrode interface.