In this work, SiO2/Nb2O5/ZnO prepared by the sol‐gel processing method was used as substrate base for immobilization of the protoporphyrin‐IX ion. Iron(III) ion was inserted into the porphyrin ring (SiNbZn‐PPFe). A simple square wave voltammetry method based on a composite sensor carbon paste electrode of this material,designed as EPC‐SiNbZn‐PPFe, was developed and validated successfully for the determination of L‐tryptophan (Trp). The optimum conditions were obtained by using sensor modified with 18.00 mg SiNbZn‐PPFe material, 12.00 mg graphite powder and 6.0 μL mineral oil and phosphate buffer 0.3 mol L−1 pH 7.0. The sensitivity of the sensor was found to be 0.523 AL mol −1, linear range from 10 to 70 μmol L−1 and limit of detection of 3.28 μmol L−1. Therefore, the developed method was successfully applied for the Trp determination in real samples of pharmaceutical formulation and can be used for routine quality control pharmaceutical formulations containing Trp.