An efficient analytical method for the preconcentration and determination of phosphate in water samples at trace levels was proposed. The method was based on sample enrichment using dispersive solid-phase extraction (dSPE) with tetraethylenepentamine (TEPA)-functionalized nano-size composite materials (TEPA-NCMs) as sorbents, which were fully characterized. Various parameters affecting the extraction efficiency were systematically investigated. After extraction, the post-adsorbed TEPA-NCMs were eluted by a NaOH solution for desorption of the phosphate. The resulting eluate containing phosphate was determined by a spectrophotometric method. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.29 and 0.96 μg L(-1), respectively. The relative standard deviations (RSDs) were lower than 8.0% with average recoveries ranging from 91 to 118%. The present method was successfully applied to the determination of phosphate at trace levels in real water samples, and it was confirmed that the TEPA-NCMs are highly effective dSPE materials.