The question is not precise. Are we talking about finite-dimensional spaces? Otherwise this is not true (indeed, for infinite dimensional cases linear operators don't even have to be continous). Also what is the differential structure on $E$ and $F$? I assume that we are talking about standard $E=\mathbb{R}^n$ and $F=\mathbb{R}^m$.
So let $f:\mathbb{R}^n\to\mathbb{R}^m$ be linear. By definition we have to find a linear operator $T:\mathbb{R}^n\to\mathbb{R}^m$ such that
$$\lim_{h\to 0}\frac{\lVert f(x_0+h)-f(x_0)-T(h) \rVert}{\lVert h\rVert}=0$$
for given $x_0\in\mathbb{R}^n$.
Put $T=f$ (note that we can do this since $f$ is linear). Then
$$\lim_{h\to 0}\frac{\lVert f(x_0+h)-f(x_0)-f(h) \rVert}{\lVert h\rVert}=\lim_{h\to 0}\frac{\lVert f(x_0) + f(h)-f(x_0)-f(h) \rVert}{\lVert h\rVert}=\lim_{h\to 0}\frac{\lVert 0 \rVert}{\lVert h\rVert}=0$$
As for the second question obviously a diffeomorphism is an isomorphism. On the other hand if $f$ is an isomorphism then $f^{-1}$ exists and is linear so by previous result it is differentiable hence $f$ is a diffeomorphism.