As an important content in fuzzy mathematics, similarity measure is used to measure the similarity degree between two fuzzy sets. Considering the existing similarity measures, most of them do not consider the hesitancy degree and some methods considering the hesitancy degree are based on the intuitionistic fuzzy sets, intuitionistic fuzzy values. It may cause some counterintuitive results in some cases. In order to make up for the drawback, we present a new approach to construct the similarity measure between two interval-valued intuitionistic fuzzy sets using the entropy measure and considering the hesitancy degree. In particular, the proposed measure was demonstrated to yield a similarity measure. Besides, some examples are given to prove the practicality and effectiveness of the new measure. We also apply the similarity measure to expert system to solve the problems on pattern recognition and the multicriteria group decision making. In these examples, we also compare it with existing methods such as other similarity measures and the ideal point method.