A novel temperature controlled ionic liquid dispersive liquid phase microextraction (TCIL-DLPME) coupled with rapid resolution liquid chromatography-electrospray tandem mass spectrometry (RRLC-ESI-MS-MS) has been developed for the enrichment and determination of three hexabromocyclododecane diastereomers (HBCDs) in water samples.Green solvent ionic liquid (IL) was used as extraction solvent instead of toxic organic solvents.This technique also avoided the usage of dispersive solvent.Some important parameters that might affect the extraction efficiency were optimized.Under the optimum conditions,good linear relationship,sensitivity and reproducibility were obtained.All the limits of detection for the three diastereomers were 0.1 ng/mL.The linear range was obtained in the range of 1-100 ng/mL for the total amount of three HBCD diastereomers.It was satisfactory to analyze real environmental water samples with the recoveries ranging from 77.2% to 99.3%.The main advantage of the method is toxic organic solvent-free.