You can define a functor $\mathcal C^\text{op}\to \mathcal D^\text{op}$ by just reversing all morphisms in sight. But a functor $\mathcal C^\text{op}\to \mathcal D$ is in general not possible.
For example, consider the category with two objects and one non-trivial map $X\to Y$. Let $F:\mathcal C\to \mathcal C$ be the identity functor on this category.
Now your concern is valid -- there's no functor $\mathcal C^\text{op}\to \mathcal C$ that remains the identity on objects but reverses the arrow, simply since there are no maps $Y\to X$.