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Homological algebra. Let $A,B$ be abelian groups (or more generally objects of an abelian category) and consider the set of isomorphism classes of abelian groups $C$ together with an exact sequence $0 \to B \to C \to A \to 0$ (extensions of $A$ by $B$). It turns out that this set has a canonical group structure (isn't that surprising?!), namely the Baer sum, and that this group is isomorphic to $\mathrm{Ext}^1(A,B)$. This is also quite helpful to classify extensions for specific $A$ and $B$, since $\mathrm{Ext}$ has two long exact sequences. For details, see Weibel's book on homological algebra, Chapter 3. Similarily many obstructions in deformation theories are encoded in certain abelian groups.

Combinatorial game theory. A two-person game is called combinatorial if no chance is involved and the ending condition holds, so that in each case one of the two players wins. Each player has a set of possible moves, each one resulting in a new game. There is a notion of equivalent combinatorial games. It turns out that the equivalence classes of combinatorial games can be made into a (large) group. The zero game $0$ is the game where no moves are available. A move in the sum $G+H$ of two games $G,H$ is just a move in exactly one of $G$ or $H$. The inverse $-G$ of a game $G$ is the one where the possibles moves for the two players are swapped. The equation $G+(-G)=0$ requires a proof. An important subgroup is the class of impartial games, where the same moves are available for both players (or equivalently $G=-G$). This extra structure already suffices to solve many basic combinatorial games, such as Nim. In fact, one the first results in combinatorial game theory is that the (large) group of impartial combinatorial games is isomorphic to the ordinal numbers $\mathbf{On}$ with a certain group law $\oplus$, called the Nim-sum (different from the usual ordinal addition). This identification is given by the nimber. This makes it possible to reduce complicated games to simpler ones, in fact in theory to a trivial one-pile Nim game. Even the restriction to finite ordinal numbers gives an interesting group law on the set of natural numbers $\mathbb{N}$ (see Jyrki's answer). All this can be found in the fantastic book Winning Ways ... by Conway, Berlekamp, Guy, and in Conway's On Numbers and Games. A more formal introduction can be found in this paper by Schleicher, Stoll. There you also learn that (certain) combinatorial games actually constitute a (large) totally ordered field, containing the real numbers as well as the ordinal numbers. You couldn't have guessed this rich structure from their definition, right?

Algebraic topology. If $X$ is a based space, the set of homotopy classes of pointed maps $S^n \to X$ has a group structure; this is the $n$th homotopy group $\pi_n(X)$ of $X$. For $n=1$ the group structure is quite obvious, since we can compose paths and go paths backwards. But at first sight it is not obvious that we can do something like that in higher dimensions. Essentially this comes down to the cogroup structure of $S^n$. There is a nice geometric proof that $\pi_n(X)$ is abelian for $n>1$.