\textit{Pursuit-evasion games} have been intensively studied for several decades due to their numerous applications in artificial intelligence, robot motion planning, database theory, distributed computing, and algorithmic theory. \textsc{Cops and Robber} (\CR) is one of the most well-known pursuit-evasion games played on graphs, where multiple \textit{cops} pursue a single \textit{robber}. The aim is to compute the \textit{cop number} of a graph, $k$, which is the minimum number of cops that ensures the \textit{capture} of the robber. From the viewpoint of parameterized complexity, \CR is W[2]-hard parameterized by $k$~[Fomin et al., TCS, 2010]. Thus, we study structural parameters of the input graph. We begin with the \textit{vertex cover number} ($\mathsf{vcn}$). First, we establish that $k \leq \frac{\mathsf{vcn}}{3}+1$. Second, we prove that \CR parameterized by $\mathsf{vcn}$ is \FPT by designing an exponential kernel. We complement this result by showing that it is unlikely for \CR parameterized by $\mathsf{vcn}$ to admit a polynomial compression. We extend our exponential kernels to the parameters \textit{cluster vertex deletion number} and \textit{deletion to stars number}, and design a linear vertex kernel for \textit{neighborhood diversity}. Additionally, we extend all of our results to several well-studied variations of \CR.

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