Step 1: Relate the charge and radius of the small and big spheres.
Let $N$ be the number of small spheres, $N=729$.
Let $r$ be the radius of a small sphere and $R$ be the radius of the big sphere.
The total volume remains constant when the spheres combine (assuming no loss).
\[
\text{Volume of big sphere} = N \times (\text{Volume of small sphere}).
\]
\[
\frac{4}{3}\pi R^3 = N \left(\frac{4}{3}\pi r^3\right).
\]
\[
R^3 = N r^3 \implies R = N^{1/3}r.
\]
For $N=729$, we have $729 = 9^3 = 9 \times 9 \times 9$. So $N^{1/3}=9$.
\[
R = 9r.
\]
Step 2: Relate the charge of the small and big spheres.
The total charge is conserved. Let $q$ be the charge of a small sphere and $Q$ be the charge of the big sphere.
\[
Q = Nq = 729q.
\]
Step 3: Relate the potential to charge and radius.
The electric potential $V$ of a charged conducting sphere is $V = \frac{1}{4\pi\epsilon_0} \frac{q'}{r'}$.
Potential of the small sphere: $V_s = \frac{1}{4\pi\epsilon_0} \frac{q}{r} = 3 \text{ V}$.
Potential of the big sphere: $V_B = \frac{1}{4\pi\epsilon_0} \frac{Q}{R}$.
Step 4: Express the potential of the big sphere in terms of the small sphere's potential.
\[
V_B = \frac{1}{4\pi\epsilon_0} \frac{Nq}{N^{1/3}r} = N^{1 - 1/3} \left(\frac{1}{4\pi\epsilon_0} \frac{q}{r}\right).
\]
\[
V_B = N^{2/3} V_s.
\]
Step 5: Calculate the potential of the big sphere.
Substitute $N=729$ and $V_s=3 \text{ V}$.
\[
V_B = (729)^{2/3} \times 3.
\]
Since $729 = 9^3$, we have $(729)^{2/3} = (9^3)^{2/3} = 9^2 = 81$.
\[
V_B = 81 \times 3 = 243 \text{ V}.
\]
\[
\boxed{V_B = 243 \text{ V}}.
\]