This is an exercise from Leinster's book:
There is a category $\textbf {Toph}$ whose objects are topological spaces and whose maps $X\to Y$ are homotopy classes of continuous maps from $X$ to $Y$. What do you need to know about homotopy in order to prove that $\textbf {Toph}$ is a category? What does it mean, in purely topological terms, for two objects of $\textbf {Toph}$ to be isomorphic?
Even though they are explicitly described, I don't understand what the arrows are. Say, in the category of topological spaces with continuous maps, there is an arrow $A\to B$ iff there is a continuous map $A\to B$. But similar description doesn't work for our case because homotopy classes of continuous maps are not maps. How should I think of arrows in this case?

In the usual category of topological spaces it is incorrect to say "there is an arrow $A\to B$ iff there is a continuous map $A\to B$". Instead, the arrows in the category are the continuous functions. There is precisely one arrow $A\to B$ for each continuous function $A\to B$. More clearly: $\mathbf{Top}(A,B)=\{f\colon A\to B\mid f \mathrm{\ is \ continuous}\}$.
Similarly then, each arrow in $\mathbf {Toph}$ is an equivalence class of continuous functions where the equivalence relation is that of being homotopic. It's not a particularly easy to imagine category.
Remark: Your confusion may stem for the terribly incorrect assumption that arrows in a category must somehow be functions. That is not the case. The objects and the arrows in a category are abstract entities. They need not be sets and functions at all.