In this study, degradation of trichloroethylene (TCE), a chlorinated hydrocarbon, using starch supported Fe/Ni nanoparticles was investigated. The scanning electron microscope images showed applying water soluble starch as a stabilizer for the Fe/Ni nanoparticles tended to reduce agglomeration and discrete particle. Also the mean particle diameter reduced from about 70 nm (unsupported Fe/Ni nanoparticle) to about 30 nm. Effects of three key independent operating parameters including initial TCE concentration (10.0–300.0 mg L−1), initial pH (4.00–10.00) and Fe0 dosage (0.10–2.00) g L−1 on TCE dechlorination efficiency in 1 hour were analysed by employing response surface methodology (RSM). Based on a five-level three-factor central composite design, TCE removal efficiency was examined and optimized. The obtained RSM model fitted the experimental data to a second order polynomial equation. The optimum dechlorination conditions at initial TCE concentration 100.0 mgL−1 were initial pH 5.77, Fe0 dosage 1.67 g L−1. At these conditions TCE removal concentration reached 94.87%, which is in close acceptance with predicted value by the RSM model.