Poly(diallyldimethylammonium) chloride, having a capability of dispersing multiwalled carbon nanotubes (MWCNTs), permits the modification of electrode surfaces. Together with putrescine oxidase, a MWCNT modified glassy carbon electrode was constructed for the development of a mediatorless putrescine biosensor. Nanoscale 'dendrites' of MWCNTs were reasoned to form a network, projecting outward from the electrode surface acting like bundled ultra-microelectrodes, thereby permitting access to the active site and facilitating direct electron transfer to the immobilized enzyme. Our biosensor was capable of efficiently monitoring the direct electroactivity of putrescine oxidase at the electrode surface. Direct electron transfer permits the detection of putrescine at negative potentials, circumventing the interference of endogenous ascorbic and uric acids, which often complicate the analysis of important compounds in plasma. Compared with the most common interfering species, such as spermine, spermidine, cadaverine, and histamine, a detection limit of 5 ?M and a response 20 times greater were found for putrescine. Tests performed on plasma of cancerous mice demonstrated that the detection of putrescine could be carried out very quickly on mammalian plasma without previous purification.