Clothianidin and (3-(1-(4-chlorophenyl)ethyl)thiazolidin-2-ylideneamino)formonitrile (NND-A) are two important Neonicotinoid insecticides. There are several methods to synthesize them, but no reference data has exposed which is necessary in industry production. So study and contrast of different routes and reaction factors should be our researsh purpose. NND-A was prepared using 1-(4-chlorophenyl)ethanone, dimethyl cyanocarbonimidodithioate and Cysteamine hydrochloride et al as raw material by four steps of reduction, halogenation, cyclization and condensation reaction, yield 80%. Metal ions unexpected catalyzed the removal of hydrogen chloride from 1-chloro-4-(1-chloroethyl)benzene. Clothianidin was prepared using (Z)-methyl-2-nitroguanidine, phenylmethanamine, and 2-chloro-5-(chloromethyl)thiazole et al as raw material by three steps of Mannich reaction, condensation and decomposition, total yield 80%. Main intermediate and productions NND-A and Clothianidin were confirmed by GC-MS, 1H NMR and X-ray diffractions. The technological process of industry production of NND-A and Clothianidin was designed on the base of research on lab scale, and the analytical method of NND-A and Clothianidin was established. The result of pilot-scale experiments indicated that the production process was reasonable, the rules of operation and safety were feasible. Thirty six novel 1-aryethyl neonicotinoid derivatives in six types of structure were designed and synthesized through bioisosterism on NND-A, Thiamethoxam, Clothianidin, Nithiazine and AKD-1022. Their structures were confirmed by means of elemental analysis, 1HNMR and crystal structure determination. Spectral properties and biological activities were also researched and some of them were found to show plant growth regulation activities. The result of bioactivity test shows that the introduction of the 1-aryethyl group destroys the conjugation system of the molecular, leading to the lower insecticidal activities on aphid.