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In this work, a systematic study of surface-enhanced Raman scattering (SERS) on TiO
2
/Ag hybrid structure is presented. TiO
2
nanofibers are synthesized by the electrospinning method and are decorated with silver nanoparticles following a simple chemical route to develop TiO
2
/Ag hybrid structure. First, SERS of rhodamine 6G is measured using the TiO
2
/Ag hybrid structure and optimized the growth conditions. The fabricated SERS substrate could detect rhodamine 6G molecules with a detection limit of 10
−14
M. The enhancement factor of the order of 10
9
is observed owing to the synergetic effect of electromagnetic enhancement and chemical enhancement. The substrate is found to be reusable owing to the photocatalytic activity of TiO
2
. The multi-analyte detection capability of SERS substrate is also studied. Also, the feasibility of using the fabricated substrates for the trace level detection of insecticide imidacloprid is demonstrated.