In this study, we developed two novel electrochemical sensors for the detection of hydroxy-α-sanshool (HαSS) and hydroxy-(α+β)-sanshool (H(α+β)SS), based on the molecularly imprinted AuNPs/Fe-MOF polymer composites films. The imprinted films were facilely constructed via in situ electrodeposition of gold nanoparticles (AuNPs) on the Fe-MOF coatings, followed by a simple electrochemical polymerization process. The AuNPs/Fe-MOF composites not only enhanced the electroactive surface areas but also improved the conductivity and the stability of the polymerized films. Under optimal conditions, the HαSS sensor demonstrated excellent performance, with a detection range of 1–120 μM and a detection limit of 0.206 μM. The sensor for H(α+β)SS, reported for the first time, exhibited a broad linear range of 0.11–132 μM and accurately detected total HαSS and HβSS, achieving a detection limit of 0.072 μM. Both sensors performed effectively in the detection of HαSS or H(α+β)SS in Zanthoxylum bungeanum Maxim. and its products. The two developed sensors significantly outperform other previously reported sanshool sensors and show previously potential for applications in the Zanthoxylum industry.