We report a facile synthesis procedure of multi-spiked star-shaped silver structures with sharp morphological features and broad plasmonic absorption for the fabrication of surface-enhanced Raman scattering (SERS) substrates. The multi-branched morphology of silver stars (AgSs) provides copious hot spots on SERS-active substrates to detect ultra-low concentrations of probe molecules. Significant Raman intensity enhancement factors of the order of ∼10 9 were obtained for the different analytes. The AgSs-based SERS-substrates show ultra-sensitive SERS performance for the detection of probe molecules rhodamine B, methylene blue, thiram, and phosmet with detectabilities 2.6 × 10 −16 , 1.97 × 10 −17 , 1.78 × 10 −18 , and 4.08 × 10 −14 M concentration, respectively. The improved SERS sensitivity originated from the additional contribution of chemical enhancement, corroborated by the appearance of new Raman bands in the SERS spectrum. For practical applications, SERS based molecule detection requires high sensitivity, specificity, uniformity, and reproducibility of the SERS signal. We demonstrate the simultaneous detection of multiple analytes, with high specificity, from the complex mixture of molecules with different compositions. The fabricated SERS substrates provide excellent signal uniformity and reproducibility with ∼10% relative standard deviation for the multiple substrates. The real-life application of AgSs-based SERS substrates with the spiked apple juice and ITO-coated PET films without pre-processing is also demonstrated.