Here we present carbon nanotube (CNT) buckypaper with efficient loading and releasing patterns for negatively charged drug. Carbonaceous membrane (Chit–NH2 /CNT) with three‐dimensionally interwoven porous nanostructure and positive surface was prepared by self‐assembly of CNT fibers hybridized with chitosan (Chit–NH2 ) in core–shell structure. Transmission electron microscopy and scanning electron microscopy images clearly showed that core–shell structured Chit–NH2 /CNT fibers and countless nanosized pores at less than 30 nm in length were formed between positively charged Chit–NH2 /CNT fibers. Based on Brunauer–Emmett–Teller N2 ‐adsorption method, the surface area, average pore size, and pore volume were approximately 19.7 m2/g, 9.54 nm, and 0.043 cc/g, respectively. Bovine serum albumin (BSA) loading and releasing profiles of these carbonaceous membrane constructed with positively charged CNT fibers were tested. The maximum entrapment of BSA was at a loading capacity of 0.65 mg/mg for 1.0 mg of Chit–NH2 /CNT hybrid membrane. The maximum release of BSA was about 65% of the entrapped amount for 1.0 mg of Chit–NH2 /CNT hybrid membrane. BSA was almost continuously released over the 11‐day period at a rate of about 0.23 g/day. Chit–NH2 /CNT hybrid membranes showing impressive drug‐loading/‐releasing characteristics could be potentially used as transdermal drug delivery system for negatively charged drugs in the medicinal field and tissue regeneration area.