This could be too broad if we're not careful. I'm sorry if it ends up that way.
Let's put together a list of different constructions of the free group $F_X$ over a given set $X$.
It seems to be one of those things a lot of people know about (and use implicitly) but whose constructions can be so tedious, it's hard to get hold of at first. The main problem, as Lee Mosher reminds us, seems to be associativity.
The Wikipedia page (linked to above) goes some way into listing some useful perspectives. I'm impressed by this intuitive summary from Wolfram:
A group is called a free group if no relation exists between its group generators other than the relationship between an element and its inverse required as one of the defining properties of a group.
But this is not exactly a construction nor is it strictly the free group over a set.
Here's a brief list of what I have so far:
This starts with the "standard" construction using finite strings over $\mathcal{X}=X\cup X'$ then asks for an opinion on quotienting by some equivalence relation.
The free group is constructed as the left adjoint of the composition of certain forgetful functors. This one is interesting in that it goes via the category InvMon of monoids with involutions as objects and involution-preserving homomorphims as morphisms.
Martin Brandenburg also gives quite a concise one in the comments there, so I invite him to elaborate on that here :)
Magnus et al. in "Combinatorial Group Theory: Presentation of Groups in Terms of Generatorators and Relations" manage to define group presentations first of all in their opening chapter.
W. Ledermann in "Introduction to Group Theory" in $\S V$ gives a very standard construction by first defining finite words over $X$, then what it means to be a reduced word, then taking $F_X$ as the reduced words over $X$ under (reduced) concatenation.
The above list is not at all exhaustive (of what I know) and there's bound to be some overlap. Personally I would be interested to see explicit use of Universal Algebra, Semigroup Theory, and Category Theory. The reason for the latter should be clear from the above; as for the first two, see
Page 68 onwards of "A Course in Universal Algebra" by Burris et al. and
Chapter 2 of "Nine Chapters on the Semigroup Art" by A.J. Cain.
Feel free to give more details on those already listed here.
The simplest definition of the elements of a free group is the one using reduced words; you found it in Ledermann. This also leads to a reasonably simple definition of the multiplication. But this just pushes the problem somewhere else, namely in verification of the associative law (once the associative law is proved, it then follows that each word is equivalent to a unique reduced word).
Personally I like a topological proof of the associative law; this will be in my book on $Out(F_n)$. One first constructs the tree $T$ whose edges are oriented and labelled by the elements of $X$, such that for each vertex $v$ and each $x \in X$ there is a unique incoming and a unique outgoing edge at $v$ labelled with $x$. After the fact one notices that this tree is the universal covering space of the wedge of circles with one circle for each generator; but you don't need the theory of universal covering spaces to construct this tree, you just construct it inductively by constructing the radius $n$ neighborhood of a base vertex, verifying as you go along that the construction satisfies the tree axiom, namely that it is connected and contains no circles. The associative law in the free group then comes down to the fact that the operation of concatenating paths and straightening the result to eliminate backtracking is an associative operation, which follows from the simple observation that two points in a tree are connected by a unique path without backtracking.