A Nafion/multi-wall carbon nanotubes (MWNTs) composite film-modified electrode was fabricated and applied to the sensitive and convenient determination of theophylline (TP). Multi-wall carbon nanotubes (MWNTs) were easily dispersed homogeneously into 0.1% Nafion methanol solution by sonication. Appropriate amount of Nafion/MWNTs suspension was coated on a glassy carbon electrode. After evaporating methanol, a Nafion/MWNTs composite film-modified electrode was achieved. TP could effectively accumulate at Nafion/MWNTs composite film-modified electrode and cause a sensitive anodic peak at around 1180 mV (vs SCE) in 0.01 mol/L H₂SO₄ medium (pH 1.8). In contrast with the bare glassy carbon electrode, Nafion film-modified electrode, Nafion/MWNTs film-modified electrode could remarkably increase the anodic peak current and decreased the overpotential of TP oxidation. Under the optimized conditions, the anodic peak current was proportional to TP concentration in the range of $8.0 \times 10^{-8}-6.0 \times 10^{-5}$ mol/L, with a detection limit of $2.0 \times 10^{-8}$ mol/L. This newly developed method was used to determine TP in drug samples with good percentage of recoveries.