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[en] Highlights: • Porous BDD/Ta sensor constructed using a Ni-assisted plasma etching method. • Sensor was applied to detection of dopamine and pyridoxine in human serum. • Electrochemical sensor has high sensitivity, selectivity, and long-term stability. • Selectivity of sensor is dependent on plane activity and surface chemistry. - Abstract: A porous boron-doped diamond (PBDD)/Ta sensing electrode was prepared for the fast, sensitive, stable, and discriminative detection of dopamine (DA) and pyridoxine (vitamin B6) in human serum. All the exposed surfaces of the diamond grains of the BDD layer were etched into a porous form, with pore sizes of less than 500 nm and an average depth of about 200 nm. The electrochemical performance characteristics of the PBDD layer and the reaction mechanisms enabling the detection of DA and vitamin B6 were studied. Large numbers of oxygen-containing groups on the PBDD surface, as well as the activity difference of the different planes, enabled us to successfully distinguish between DA and B6 by using the PBDD/Ta electrode. The low background current of PBDD, the large active area of the porous surface, and the high electron transfer properties led to the PBDD electrode having a high sensitivity. Therefore, this sensor can be used to stably detect DA and B6 in serum. Aberrant levels of DA and vitamin B6 in body fluids are key risk indicators for some diseases; thus, monitoring the levels of both and other species in serum is of great significance to clinical diagnoses.