Direct electrochemistry of hemoglobin (Hb) entrapped in the dextran (De) film on the surface of a room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) modified carbon paste electrode (CILE) has been investigated. UV-Vis and FT-IR spectroscopy showed that Hb retained its native structure in the De film. Scanning electron microscopy (SEM) indicated an uniform film was formed on the electrode surface. Cyclic voltammetric experiments indicated that the electron transfer efficiency between Hb and the electrode was greatly improved due to the presence of the De film and ionic liquid, which provided a biocompatible and higher conductive interface. A pair of well-defined and quasi-reversible redox peak was obtained with the anodic and cathodic peaks located at -0.195 V and -0.355 V in pH 7.0 phosphate buffer solution, respectively. The electrochemical parameters were calculated by investigating the relationship of the peak potential with the scan rate. The fabricated De/Hb/CILE showed good electrocatalytic ability to the reduction of H₂O₂ with the linear concentration range from $4.0 \times 10^{-6}$ to $1.5 \times 10^{-5}$ mol/L and the apparent Michaelis-Menten constant ($K_M^{\text{app}}$) for the electrocatalytic reaction was calculated as 0.17 𝜇M.