In this paper, we demonstrate the effects on the second largest eigenvalue $λ_2(G)$ of a connected graph $G$ after edge addition or deletion. In 1989, Chung, Graham and Wilson showed $\max\{|λ_2|,|λ_n|\}>Ω(n)$ for dense $K_{r+1}$-free graphs of order $n$, giving spectral comprehension of existence of large clique or independent set, respect to Ramsey theory. Applying the results of effects on $λ_2$ after edge operations, we determine the maximum value of $λ_2$ among all $K_{r+1}$-free connected graphs with given order, and completely characterize the extremal graphs. Moreover, for arbitrary given graph $F$, we investigates the maximum second largest $λ_2(G)$ among $F$-free connected graphs of order $n$. Let $ρ^*(n,F)$ be the maximum spectral radius of $F$-free graphs on $n\ge n_F$ vertices, and $G^*(n,F)$ be a graph with its spectral radius $ρ\big(G^*(n,F)\big)=ρ^*(n,F)$. We prove that, for an $F$-free connected graph $G$ of order $n\ge f(n_F)$, \\(1) if $n$ is odd, then $$λ_2(G)\leρ^*\left(\frac{n-1}{2},F\right)$$ with equality if and only if $G\in \mathcal{I}\big(G^*(\frac{n-1}{2},F),G^*(\frac{n-1}{2},F)\big)$; and\\ (2) if $n$ is even, and $F$ does not contain cut edges, then the graph $G^†$ with the maximum second largest eigenvalue satisfies $$λ_2(G^†)=ρ^*\left(\frac{n}{2},F\right)-o(1)$$ and $G^†\in \mathcal{E}\big(H_1,H_2\big)$, where $H_1$ and $H_2$ are $F$-saturated graphs on $\frac{n}{2}$ vertices. In particular, other than a complete graph $K_{r+1}$, when $F$ is a book graph $B_{k+1}$ or an odd cycle $C_{2k+1}$, we are able to determine the maximum second largest eigenvalue for $F$-free connected graphs of given order, and completely characterize the extremal graphs.