Extremal problems related to the enumeration of graph substructures, such as independent sets, matchings, and induced matchings, have become a prominent area of research with the advancement of graph theory. A subset of vertices is called a dissociation set if it induces a subgraph with vertex degree at most $1$, making it a natural generalization of these previously studied substructures. In this paper, we present efficient tools to strictly increase the number of dissociation sets in a connected graph. Furthermore, we establish that the maximum number of dissociation sets among all connected graphs of order $n$ is given by \begin{align*} \begin{cases} 2^{n-1}+(n+3)\cdot 2^{\frac{n-5}{2}}, &~ {\rm if}~ n~{\rm is}~{\rm odd};\\ 2^{n-1}+(n+6)\cdot 2^{\frac{n-6}{2}}, &~ {\rm if}~ n~{\rm is}~{\rm even}. \end{cases} \end{align*} Additionally, we determine the achievable upper bound on the number of dissociation sets in a tree of order $n$ and characterize the corresponding extremal graphs as an intermediate result. Finally, we identify the unicyclic graph that is the candidate for having the second largest number of dissociation sets among all connected graphs.