We present a novel approach for the synthesis of silver nanoparticles capped with oleylamine (AgNPs/OLA) and its application in conductive ink for electroanalytical application. The synthesized OLA capped AgNPs was characterized with TEM, UV-Vis, EDX, FTIR and TGA to confirm the size, composition and surface modification of NPs. In this paper, we report conductive ink printing using a pen to achieve a best conductivity value of 0.11×105 Scm−1. A 10wt% AgNPs nano-ink solution was used for printing conductive electrodes (counter, reference and working) on-to photo paper and sintered at 150°C for 1h to achieve metallization. We demonstrated successful application of printed conductive electrodes in cyclic voltammetry (CV) measurement. To ensure the continuity of conductive pattern, we demonstrated the lighting of LED when conductive track was connected to a 9V battery. This report shows that paper-based flexible electrodes are user-friendly, cost effective and useful for multiple analyses in CV compared to other printed electrodes.