A facile synthetic protocol for the electrodeposition of diverse morphologies of silver on disposable pencil graphite electrodes (Ag/PGE) in the presence of chitosan as structure-directing agent (SDA) is reported. The influence of various electrodeposition parameters on the morphology of Ag deposited has been studied and interpreted using electron microscopic techniques. Several impressive morphologies such as hexahedron, leaf and dendrites have been observed for Ag/PGE with respect to change in experimental conditions. Furthermore, the crucial role of chitosan in determining the morphology of Ag/PGE has been elucidated with the help of three-dimensional Scharifker-Hills nucleation and growth model. The electrocatalytic activities of various Ag/PGEs towards the reduction of hydrogen peroxide (HP) and oxidation of hydrazine hydrate (HH) have been studied in detail with the help of diverse electrochemical techniques. In comparison with PGE, the Ag hexahedron- (Ag-Hex/PGE) and Ag dendrite- (Ag-Dend/PGE) modified PGEs exhibited excellent electrocatalytic activity towards HP and HH, respectively. The Ag-Hex/PGE displayed a wide linear range of 0.1–20,000 μM with a limit of detection (LOD, 3σ/m) of 0.06 μM for HP reduction. On the other hand, a linear range of 25–20,000 μM with LOD of 1.8 μM for HH oxidation has been observed for Ag-Dend/PGE. Furthermore, the modified Ag/PGEs revealed remarkable reproducibility and long-term storage stability. The practical applicability of the Ag-Hex/PGE and Ag-Dend/PGE was demonstrated through the electrocatalytic detection of HP in milk and HH in tap water samples with satisfactory recovery results. © 2020, Springer-Verlag GmbH Germany, part of Springer Nature.