In this study, magnetic metal-organic framework composite (Fe3O4@ TMU-12) was fabricated and used as an efficient sorbent for magnetic solid-phase extraction of the diazinon and chlorpyrifos from environmental water samples. By simultaneous use of magnetic solid-phase extraction and high-performance liquid chromatography, a simple, quick, exact, and affordable method for the determination of diazinon and chlorpyrifos was achieved. The extraction conditions and efficiency of the magnetic framework composite for diazinon and chlorpyrifos were investigated. Under optimal conditions, the relative recoveries and preconcentration factors of the studied compounds were obtained in the range of 92.0%–99.3% and 201–210, respectively. The calibration curves were obtained in the range of 2–250 μg L−1 and 4–250 μg L−1 for diazinon and chlorpyrifos in water samples, respectively. The LODs were 0.5 and 0.8 μg L−1 for diazinon and chlorpyrifos, respectively (based on S/N = 3). The precision evaluated in terms of the relative standard deviations of intra- and inter-day tests ranged from 3.4% to 3.8% and from 3.9% to 4.1%, respectively. The results show that the Fe3O4@TMU-12 combine advantages of magnetic nanoparticles and metal-organic frameworks, and are the promising sorbents in the magnetic solid-phase extraction of diazinon and chlorpyrifos from environmental water samples.