On trees of fixed order, we show a direct relation between Kemeny's constant and Wiener index, and provide a new formula of Kemeny's constant from the relation with a combinatorial interpretation. Moreover, the relation simplifies proofs of several known results for extremal trees in terms of Kemeny's constant for random walks on trees. Finally, we provide various families of co-Kemeny's mates, which are two non-isomorphic connected graphs with the same Kemeny's constant, and we also give a necessary condition for a tree to attain maximum Kemeny's constant for trees with fixed diameter.