The ability to deal with major emergencies is an important part of the national governance system and governance capabilities, and it is also an important manifestation of the modernization of national governance capabilities. Volunteer service, as an important element of social governance in the new era, also plays a unique role in responding to major emergencies. However, judging from the current situation of responding to major emergencies in recent years, it is difficult for volunteer services to meet the needs of emergency work in terms of quality and quantity. For example, most volunteers are in lack of experience in dealing with major emergencies, and even without professional training. In reviewing the lessons learnt from the typical cases of major emergencies in recent years and actual investigations in disaster areas, in this paper we proposed the following countermeasures to improve the ability, i.e. following the rule of law for volunteer services to participate in emergency;strengthening the professional construction capacity of "combining peacetime with wartime";enhancing the linkage coordination ability of "Internet+" multi-party cooperation;and formulating the precise incentive guarantee ability of volunteer participation in emergency. These above countermeasures are helpful for solving the dilemma of volunteer participation in major emergencies.