In the present paper an amperometric sensor based on graphite-SiO2/Al2O3/Nb2O5-methylene blue (GRP-SiAlNb-MB) composite has been successfully prepared for dopamine (DA) determination in real samples. The electrochemical behavior of DA at the GRP-SiAlNb-MB has been evaluated by employing cyclic voltammetry. The best ratio (m/m) of GRP-SiAlNb-MB composite was found to be 1:0.54. Under optimized conditions (pH 7.5 in 0.15 mol L−1 phosphate buffer) the amperometry method responds linearly to DA from 5.0 up to 500.0 μmol L−1 (r = 0.995) with limits of detection and quantification of 1.49 and 4.97 μmol L−1, respectively. The developed method was successfully applied for DA determination in real samples of pharmaceutical formulations and can be used for routine quality control analysis of pharmaceutical formulations containing DA. The use of inorganic matrix SiAlNb was found to be very useful to adsorb MB in the composite material with further improvement of the anodic peak current of DA.