Here are some examples I've used (class examples, homework, tests, etc.):
Let $G = \{x \in \mathbb R: x \neq -1\}$ and define $*$ by $a*b=a+b+ab$.
Fix an integer $k$. Let $G = \mathbb Z$ and define $*$ by $a*b = a + b + k$.
Fix a real number $\beta > 0$. Let $G = \{x \in \mathbb R: x > 0 \}$ and define $*$ by $a*b = \beta ab$.
Let $G = \{x \in \mathbb R: -1 < x < 1 \}$ and define $*$ by $a*b = \frac{a+b}{1 + ab}$.
Let $G = \mathbb R$ and define $*$ by $a*b = \sqrt[3]{a^{3}+b^{3}}$.
More examples can be obtained by the following general methods:
Let $(G,\bullet)$ be a group and fix $g \in G$. Then $(G,*)$ is a group, where $*$ is the operation defined by $a*b = a \bullet g \bullet b$.
Let $(G,\bullet)$ be a group and $f:G \rightarrow G$ be a 1-1 and onto (i.e. bijective) function. Then $(G,*)$ is a group, where $*$ is the operation defined by $a*b = f^{-1}\left(f(a) \bullet f(b) \right)$.
If we go outside the realm of real numbers for the set $G$, then far more exotic examples are possible. For example, let $X$ be any set and let $P(X)$ be the set of subsets of $X$. Then $\left( P(X),\Delta \right)$ is a group, where $\Delta$ is the symmetric difference operation defined by $A \Delta B = (A-B) \cup (B-A)$. For another example, let
$$G = \left\{ x, \frac{x + 5}{3 - x}, \frac{x - 5}{x-1}, \frac{3x-5}{x+1} \right\},$$
whose elements are functions from ${\mathbb R} - \{-1,1,3\}$ into ${\mathbb R} - \{-1,1,3\}.$ Then $(G,*)$ is a group, where $*$ is the operation of composition of functions.