The complex eigenvalues of a Rotation matrix are $e^{-i\theta}$ and $e^{i\theta}$. Corresponding to these we get complex eigenvectors.
We know that the eigenvector corresponding to the eigenvalue 1 is the axis of rotation. How to prove that the $\theta$ from complex eigenvalues is the angle of rotation.
Comparing it with some Rotation matrix for rotation about x,y or z axis is easy, but how to conclude this for a generic R belonging to SO(3).
Suppose $e^{i\theta}\neq e^{-i\theta}$. I leave to you the case $e^{i\theta}=e^{-i\theta}$.
Let $v=v_1+iv_2$ be a column vector of $\mathbb{C}^3$ such that $Rv=e^{i\theta}v$, where $v_1,v_2\in\mathbb{R^3}$ (Prove that $v_1\neq 0$ and $v_2\neq 0$). Let $v^t$ be its transpose.
Now, $R^tR=Id$ then $v=R^tRv=e^{i\theta}R^tv$. So $R^tv=e^{-i\theta}$.
Next, $e^{i\theta}v^tv=v^tRv=(v^tRv)^t=v^tR^tv=e^{-i\theta}v^tv$.
Since $e^{i\theta}\neq e^{-i\theta}$ then $0=v^tv=|v_1|^2-|v_2|^2+i2(v_2^tv_1)$. So $|v_1|=|v_2|$ and $v_1\perp v_2$. Without loss of generality assume $|v_1|=|v_2|=1$.
Now, $R(v_1)+iR(v_2)=R(v_1+iv_2)=(cos(\theta)+isin(\theta))(v_1+iv_2)=$ $(cos(\theta)v_1-sin(\theta) v_2)+i(sin(\theta) v_1+cos(\theta)v_2)$.
So $R(v_1)=(cos(\theta)v_1-sin(\theta) v_2)$ and R$(v_2)=(sin(\theta) v_1+cos(\theta)v_2)$.
Let $W$ be the plane generated by $v_1,v_2$.
Finally, the matrix of the restriction of R to $W$ relative to the orthonormal basis $v_1,v_2$ is $\left(\begin{array}{cc} cos(\theta) & sin(\theta) \\ -sin(\theta) & cos(\theta) \end{array}\right) $.