Permethrin, 3-Phenoxybenzyl (1 RS)-cis,trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylate, has a wide range of applications like insecticide, insect repellent and prevents mosquito-borne diseases, such as dengue fever and malaria in tropical areas. In this work, we develop a prominent monitoring method for the detection of permethrin pesticide using surface-enhanced Raman scattering (SERS) optical fibre substrates. The novel SERS-active optical fibre substrates were grown and deposited silver (Ag) nano-dendrites on the end of multi-mode fibre core by laser-assisted photochemical method. The characteristic of the Ag-nanostructures could be controlled by the experimental conditions, namely, laser illumination time. Ag nanoparticles optical fibre substrates and Ag nano-dendrites optical fibre substrates were prepared with laser illumination time of 3 min and 8 min, respectively. The achieved SERS-activity optical fibre substrates were tested with Rhodamine 6G aqueous solutions. We demonstrate that the SERS activity coupled with Ag nano-dendrites optical fibre substrate has higher Raman enhancement factor due to the creation of many of hot-spots for amplifying Raman signals. Besides, the stability and reproducibility of the Ag nano-dendrites optical fibre substrate were also evaluated with stored time of 1000 hours and relative standard deviation of less than 3%. The Ag nano-dendrite optical fibre substrate was selected for detection of permethrin pesticide in the concentration range of 0.1 ppm-20 ppm with limit of quantification (LOQ) of 0.1 ppm and calculated limit of detection (LOD) of 0.0035 ppm, proving its great potential for direct, rapid detection and monitoring of permethrin.