For a fixed positive integer $k$ and a graph $G$, let $λ_k(G)$ denote the $k$-th largest eigenvalue of the adjacency matrix of $G$. In 2017, Tait and Tobin proved that the maximum $λ_1(G)$ among all outerplanar graphs on $n$ vertices is achieved by the fan graph $K_1\vee P_{n-1}$. In this paper, we consider a similar problem of determining the maximum $λ_2$ among all connected outerplanar graphs on $n$ vertices. For $n$ even and sufficiently large, we prove that the maximum $λ_2$ is uniquely achieved by the graph $(K_1\vee P_{n/2-1})\!\!-\!\!(K_1\vee P_{n/2-1})$, which is obtained by connecting two disjoint copies of $(K_1\vee P_{n/2-1})$ through a new edge joining their smallest degree vertices. When $n$ is odd and sufficiently large, the extremal graphs are not unique. The extremal graphs are those graphs $G$ that contain a cut vertex $u$ such that $G\setminus \{u\}$ is isomorphic to $2(K_1\vee P_{n/2-1})$. We also determine the maximum $λ_2$ among all 2-connected outerplanar graphs and asymptotically determine the maximum of $λ_k(G)$ among all connected outerplanar graphs for any fixed $k$.