Not a particularly flashy example, but consider the function $f: \mathbb{R}\to \mathbb{R}$ given by
$$
f(x) = \begin{cases}
x+2x^2\sin(\frac{1}{x})&\text{if }x\neq 0\\
0&\text{if }x=0
\end{cases}.
$$
You can show that $f$ is differentiable on all of $\mathbb{R}$ with $f'(0) = 1$, but $f'$ is discontinuous at 0. To see that $f$ is not a local diffeomorphism at the origin, you can find a sequence of intervals that approach the origin on which $f$ is decreasing, but since $f'(0)>0$ we can find a point $a$ with $0<a$ with $f(0)<f(a)$, so $f$ can't be a one-to-one mapping on any neighborhood of zero.
In detail, we have
$$
f'(x) = \begin{cases}
1 + 4x\sin(\frac{1}{x})-2\cos(\frac{1}{x})&\text{if }x\neq 0\\
1&\text{if }x=0
\end{cases}.
$$
As $x$ approaches 0 the $4x\sin(\frac{1}{x})$ term can be made arbitrarily small while the $2\cos(\frac{1}{x})$ term oscillates between $-2$ and $2$. Consequently, we can find a sequence of points $x_n\to 0$ with $0<x_{n+1}<x_n$ such that $f'(x_n) = -1$ say. Since $f'$ is continuous away from the origin, $f$ is decreasing on a small neighborhood of each $x_n$ by the mean value theorem.
By the definition of the derivative we have
$$
f'(0) = \lim_{x\to 0}\frac{f(x)-f(0)}{x-0} = \lim_{x\to 0}\frac{f(x)}{x} = 1>0.
$$
In particular, for $a$ sufficiently close to zero and positive we have $f(a)>0$. Now if we take one of our $x_n$'s such that $0<x_n<a$ then $f$ is decreasing on some interval contained in $(0, a)$. But if $f(0)=0$, $f(a)>0$, and $f$ is decreasing on some interval between $0$ and $a$ then by continuity, $f$ can't be one-to-one on $[0,a]$.