A new molecularly imprinted polymer–multiwall carbon nanotube paste electrode (MIP–MWNPE) was prepared as a voltammetric sensor for rutin. The electrochemical behavior of rutin at the surface of the modified electrode was studied using cyclic voltammetry (CV) and square wave voltammetry (SWV). Under the optimized conditions, the oxidation peak current of rutin showed two linear dynamic ranges (0.08–1.4 μM and 2.0–160.0 μM) with a detection limit of 0.05 μM, using square wave voltammetric method. The RSD% for 5.0 and 10.0 μM determination of rutin were 2.7% and 2.9%, respectively. The kinetic parameters such as electron transfer coefficient (α) and charge transfer rate constant (k_s/s⁻¹) were also determined using the electrochemical approach. The modified electrode showed good sensitivity, special selectivity, and stability for rutin analysis. It was successfully applied for the determination of rutin in real samples such as urine and pharmaceutical formulation with satisfactory results.