Selectivity and enhanced sensitivity for surface-enhanced Raman scattering (SERS) substrates are highly desirable attributes for their analytical applications. SERS substrate interaction with target molecules plays a key role in determining the enhancement magnitude and spectral profile of the SERS signal as well as their applications. Herein, we demonstrate a SERS active substrate based on reduced graphene oxide/silver nanoparticles (rGO/Ag NPs) composite material synthesized by a facile wet chemical route. The Ag NPs decorated rGO nanosheet has been achieved by reducing AgNO3 with ethylene glycol in the presence of poly vinyl pyrrolidone (PVP) and NaCl over layered graphene oxide. The addition of PVP stimulates the nano-phase growth as well as uniform distribution of the Ag NPs on rGO nanosheet. The well synthesized rGO/Ag composite was confirmed by using various characterization techniques such as FESEM, HRTEM, XRD, FTIR and Raman. Further, the rGO/Ag NPs composite material has been utilized as a platform for SERS based selective detection of Rhodamine-6G, 4-mercapto benzoic acid, and 2,4-dinitrotoluene analytes. The rGO/Ag NPs substrate demonstrates good homogeneity, stability and nanomolar sensitivity with Raman intensity enhancement of the order of 5 for Rh-6G and 4-MBA whereas 3 for 2,4-DNT. The observed enhancement of SERS signal for all the analytes has been attributes to the cumulative effect of rGO and Ag NPs. Display omitted •We fabricated and demonstrated a generic SERS sensor based on Ag-rGO composite.•Wet chemical process has been used for the decoration of spherical silver nanoparticles on the rGO nano sheets.•The loading density of the Ag NPs on rGO nanosheet depends on AgNO3 molar concentration.•The optimized concentration of AgNO3 and GO for highest enhancement in Raman intensities was 0.01M and 2.5mg respectively.•Synthesized nanocomposite acts as SERS sensitive substrate for the detection of Rh-6G, 4-MBA, and 2,4-DNT up to the nM range.•The enhancement factors are found to be 5 orders of magnitude for Rh-6G, 4-MBA and 3 orders of magnitude for 2,4-DNT.