"Unusual" coupling between a decision problem and a corresponding optimization problem
The answer does indeed depend on how you define a "corresponding" problem.

For example, it is well known 2-SAT is easy ("Given a 2-SAT formula, is it satisfiable?"). However, the optimization problem MAX-2-SAT ("Given a 2-SAT formula, find an assignment maximizing the number of clauses") is NP-hard. Even MIN-2-SAT is NP-hard.

For a given decision problem, you can have "corresponding" optimization problems which are either easy or hard, depending on whether we consider a minimization or a maximization problem. The st-connectivity problem is mentioned in the comments: deciding the existence of such a path is easy, finding a shortest st-path is easy, but finding a longest st-path is hard. Another graph theoretic example is with cuts: computing a minimum cut is easy, but computing a maximum cut is again hard.

You also have decision problems that don't have a corresponding optimization problem, such as primality testing.