A microfluidic device utilising the flow focusing method was designed and fabricated for the high-throughput and controllable preparation of millimeter-scale water-in-oil (W1/O/W2) droplets. Two distinct flow focusing modes were employed in order to prepare the composite droplets. In the flow-focused axisymmetric jetting mode, the continuous phase propels the dispersed phase, forming a cone, which subsequently leads to a jet formation downstream of the small hole. When the outer phase is activated, perturbation growth interferes with downstream fragmentation, resulting in composite droplets with excellent monodispersity. In the dripping mode, the dispersed phase fails to form a jet downstream, and the interface disintegrates, resulting in droplet formation at the exit of the small orifice. In the jetting mode, the size and shell-to-core ratio of the generated droplets can be controlled by adjusting the volume of flow of the outer and inner phases, as well as the applied frequency. Furthermore, the applied perturbation allows for precise control of droplet size, which significantly reduces satellite droplet formation and enhances droplet monodispersity. In the dripping mode, the shell-to-core ratio is adjusted by manipulating the ratio of inner to outer flow rates, which is tailored to the specific requirements of the flow-focused dripping mode. The prepared compound droplets exhibit good monodispersity. Finally, the rotational solidification method can be employed to obtain spherical shells with a shell thickness of less than 20 μm. In conclusion, the flow focusing method is an effective, controllable, and stable method for synthesising millimetre-sized composite droplets.