The development of non-enzymatic and binder-free biosensors plays a vital role, and it possesses main benefits for effective biomolecule recognition with high sensitivity and preferred selectivity. Herein, an atomic layer deposition (ALD) was employed to develop the hafnium oxide (HfO2) nanofilm on silicon (Si) for fabricating binder-free selective and sensitive determination of the non-enzymatic electrochemical dopamine sensor. The prepared HfO2 nanofilm selectively acted as a local dopamine binding site because of the hydrophobic-hydrophobic interaction between fabricated film and dopamine, electrostatic attraction between negatively charged hydroxyl group on film surfaces, and positively charged amino group of dopamine. The developed insufficient oxygen vacancies on the HfO2 could have behaved as a charge-trapping site for better sensing properties. The developed sensor demonstrated excellent realization in sensing dopamine with a very low detection limit (0.4 pM) and swift response time of 3s which is quite precise compared with various reported literature. The fabricated HfO2/Si electrode sensor has exhibited high sensitivity, stability, and repeatability. The selectivity of dopamine sensors was at least three orders greater than other interfering biomolecules. This work proposes the essential track for the practical realization of dopamine detection in human serum and biomedical applications.