Recent advent of Aqueous-Two-Phase-System (ATPS), more biologically friendly compared to conventional oil-water systems, has shown great potential to rapidly generate aqueous droplets without tedious post-processing. However, understanding of underlying physics of droplet formation in ATPS is still in its infancy. In this paper, we investigate hydrodynamic behaviors and mechanisms of all-aqueous droplet formation in two flow-focusing droplet generators. Two incompatible polymers namely polyethylene glycol (PEG) and dextran (DEX) are mixed in water to make ATPS. The influence of inlet pressures and flow-focusing configurations on droplet sizes, and thread breakup length is studied. Flow regime mapping for two different configurations of droplet generators possessing junction angles of 30° and 90° is also obtained. The results show that droplet size is very susceptible to the junction angle while inlet pressures of the PEG and DEX flows readily control four main flow regimes including back flow, dripping, jetting and stratified.