The relative entropy measure quantifying coherence, a key property of quantum system, is proposed recently. In this note, we firstly investigate structural characterization of maximally coherent states with respect to the relative entropy measure. It is shown that mixed maximally coherent states do not exist and every pure maximally coherent state has the form U|ψihψ|U† , |ψi = √1 d Pd k=1 |ki, U is diagonal unitary. Based on the characterization of pure maximally coherent states, for a bipartite maximally coherent state with dA = dB, we obtain that the super-additivity equality of relative entropy measure holds if and only if the state is a product state of its reduced states. From the viewpoint of resource in quantum information, we find there exists a maximally coherent state with maximal entanglement. Originated from the behaviour of quantum correlation under the influence of quantum operations, we further classify the incoherent operations which send maximally coherent states to themselves.