The invention discloses an apparatus and a method for detecting a combination process of odorant-binding protein and pheromone. The apparatus comprises a sample introduction system, a measure transition system, a counter electrode, a reference electrode, a working electrode, a measure groove, an oscillator, a liquid-outlet peristaltic pump, a waste liquid groove and a computer; the sample introduction system consists of a first peristaltic pump, a second peristaltic pump, a third peristaltic pump, a first injector, a second injector, a third injector and a controller; and the measure transition system consists of a measure circuit, a high-resistance electrometer and a measure circuit. The method comprises preparing honeybee pheromone isoamyl-acetate standard solutions with different concentration, an apis-cerana-ceraca odorant-binding protein (Acer-ASP2) standard solution, and mixed solutions of apis-cerana-ceraca odorant-binding protein (Acer-ASP2) and honeybee pheromone isoamyl acetate and with different concentration, and detecting variation of electrochemical impedance of the three kinds of solutions along with time, so as to obtain corresponding electrochemical impedance spectrograms, and further to obtain the combination of odorant-binding protein and pheromone.