A new, simple, rapid and efficient solvent terminated-auxiliary solvent-dispersive liquid-liquid microextraction (ST-AS-DLLME) technique for determination of cyanide ions by microvolume UV-Vis spectrophotometry was developed. Effective parameters on the extraction and absorbance of cyanide were optimized using two optimization methods: fractional factorial design (FFD) and central composite design (CCD). Zinc(II) tetraphenylporphyrine (ZnTPP) was used as a selective cyanide receptor agent. Methyl isobutyl ketone (MIBK), ethanol and 1-butanol were used as extraction solvent, dispersive solvent and demulsifier solvent, respectively. The method shows very good selectivity in presence of other species. The analytical curve was linear in the range of 4.0-130 μg L-1 with a limit of detection of 1.0 μg L-1. Relative standard deviation (RSD) of the method for ten replicate measurements of 100 μg L-1 of cyanide was 1.1%. The method was successfully applied for determination of cyanide in natural water and plasma samples with good spike recoveries
