The dynamic characteristics and the estimation method of operational availability under general mission scenarios are researched. Though the simulation method can be used to study the time-varying operational availability, it has shortage in finding and analyzing the inherent law of operational availability. According to definition, the operational availability can be derived by the supply availability and achievable availability, and so the transformation character of operational availability can be derived on the research of supply availability and maintenance availability. In order to solve this problem, the authors study the characteristics of supply availability and maintenance availability on the requirements of mission scenarios. The dynamic characteristics of operational availability are derived and the estimation method of time-varying availability is given. Further, the time of operational availability reaching stationary value is obtained. Once the problem is solved, a profit comparison is also made between the analytical method described in this paper and the simulation method to observe whether the analytical approach incorporates mission scenarios in the time-availability. Experiments show that the model works well, and so the feasibility and rationality of the analytical method are validated. This result establishes good base for further research in relative problems.