We can view harmonic function $u(x,y,z)$ as a wave function that does not depend on time $t$. Let $\overline{u}(r)$ be its average value on the circle with radius $r$.
Assume we have proved that it satisfies $0=(\overline{u})_{rr}+2\frac{1}{r}(\overline{u})_r$.
I think it remains to show that $\overline{u}$ is constant so that $\overline{u}$ equals $u(0)$, which is equivalent to show $(\overline{u})_r=0$. We can see $0$ is one solution of the ODE, but I cannot disprove that others are not.
Any hints would be appreciated!
Let $v=\overline{u}$.
$v_{rr}+\frac{2}{r} v_r=0$, so $\frac{d}{dr} \left ( e^{2 \log(r)} v_r \right ) =0$, so $r^2 v_r=C$, so $v_r=\frac{C}{r^2}$, so $v=C/r+A$.
This is the general solution to the equation on any interval not containing $r=0$. This means that if you delete the origin, then there is a nonconstant radial function which satisfies the ODE. However, this function is singular at the origin. If you assume the function is not singular at the origin, then you must have $C=0$ in which case $v=A$ as desired.
Note that this singular solution does not furnish any contradiction to the mean value theorem as it is correctly formulated (the domain of the harmonic function must contain the entire ball whose boundary is the sphere in question).