This paper reports the fabrication of carboxymethyl chitosan (CMCH) nanofibers containing Doxorubicin anti-cancer drug and studies the controlled release of Doxorubicin from the electrospun nanofibrous CMCH matrix. CMCH-Doxorubicin nanofibrous mats were electrospun from solutions containing 16.7, 25 and 34% (W/W) Doxorubicin. The diameter of the electrospun nanofibers lied in the range of 390-460 nm. It was found that increasing the share of Doxorubicin leads to higher diameter of the electrospun nanofibers. Fourier transform infrared spectroscopy analysis showed no reaction between Doxorubicin and carboxymethyl chitosan. X-ray diffractions showed that Doxorubicin was distributed as crystallites in the crystalline CMCH matrix. High performance liquid chromatography investigations proved that CMCH nanofibers containing Doxorubicin have the capability of controlled release of the drug. It was also found that depending on the amount of Doxorubicin in the CMCH matrix, the release of the drug occurs according to non-Fick or Fick diffusion mechanism.