In this work, a new coupling of spectrophotometric determination with preconcentration method named as ultrasound-assisted emulsification dispersive liquid-liquid microextraction (UAE-DLLME) for trace silver was firstly established. Disperser solvent in traditional DLLME was substituted by ultrasound-assisted emulsification, which could afford more effective emulsification and make the extraction method greener. The extraction was accomplished efficiently in only 3 min during ultrasound-assisted emulsification. Compared to traditional DLLME, the established pretreatment was simpler, greener and more effective. The UAE-DLLME technique was effectively coupled with ordinary spectrophotometer to improve the analytical performance and expand the application of spectrophotometric determination. The factors influencing UAE-DLLME, such as concentration of chelating agent, kind and volume of extractant, pH, conditions of phase separation, ultrasound extraction time and instrumental conditions, were studied in detail. Under the optimal conditions, the limit of detection (LOD) for silver was 0.45 μg L(-1), with sensitivity enhancement factor (EF) of 35. The established method was applied to the determination of trace silver in real and certified reference samples with satisfactory analytical results.