Demulsification is an important process for dehydration of crude oil and environmental remediation. The intrinsic structure of metal-organic frameworks (MOFs) endows MOFs with amphipathicity and meets the requirement of demulsifier. Herein, we studied the demulsification performance, process and characteristic using MIL-100(Fe). The amphipathicity of MIL-100(Fe) is crucial for demulsification. The demulsification efficiency (DE) for model emulsion excessed 99% within 30 min at optimal condition, and dehydration efficiency for crude oil emulsion was up to 79% within 5 min. The DE can be maintained when the pH ranged from 10.0 to 4.0, and it increased along with an increase of salinity (1~1000 mmol•L-1). Component analysis revealed that the degradation of sodium dodecyl sulfonate occurred by an abstraction of SO32-, which could eliminate the potential risk of emulsifying again. Therefore, this study confirmed that enhancing the interaction with emulsion is an effective strategy for new demulsifier to against the harsh conditions.