The development of a proficient and ultra-high sensitive functionalized electrode for accurate analysis of drugs is a long-standing challenge. Herein, we report an electrochemical nanocomposite scaffold, comprising of silver nanoparticles integrated with functionalized carbon nanotubes (COOH-CNTs/Ag/NH₂-CNTs) for the simultaneous quantification of two widely used amlodipine (AM) and atorvastatin (AT) drugs. The sandwiched nanocomposite materials were thoroughly characterized morphologically and structurally. The nanocomposite COOH-CNTs/Ag/NH₂-CNTs immobilized over glassy carbon electrode catalyzed electron transfer reactions at the electrode–electrolyte interface and facilitated detection of targeted drugs, as revealed by the significant decrease in oxidation potentials at 879 mV and 1040 mV and improved current signals. Electrochemical characterization and testing show that the functionalized porous architecture with a large effective surface area is a promising scaffold for the sensing of a binary mixture of AM and AT with limits of detection in the femtomolar range (77.6 fM, and 83.2 fM, respectively). Besides, the specificity, stability, and reliability of the electrochemical sensing platform in simple and complex biological and pharmaceutical samples with high percentage recoveries highlight its scope for practical applications. Computational studies supported the experimental outcomes and offered insights about the role of modifier in facilitating electron transfer between transducer and analytes.