We could do this conventionally by using Cantor's diagonal slash argument. This is almost certainly the best way for those new to (un)countability to understand why it's true. But once you have a little more familiarity with the subject matter, I think that the following proof is both unusual and entertaining.
Let's prove this by playing a game! Actually, let's let Bob and Alice play a game, using the interval $[a,b]$. (although it works equally well if they play with $(a,b)$
Suppose we have the interval $[a,b]$ and a set $S$. In the game, Alice begins, and she chooses some $a_1 \in(a,b)$ to act as a new lower bound and tells Bob what it is. Bob then chooses some $b_1 \in (a_1,b)$ to act as a new upper bound and tells Alice. Alice then picks $a_2 \in (a_1,b_1)$, and they carry on taking turns in this manner, producing smaller and smaller intervals.
Now, $a_n$ is an increasing, bounded sequence in $\mathbb{R}$ so we know it converges, say to $a' \in (a,b)$.We say that Alice wins the game if $a'\in S$ and Bob wins otherwise. A question arises, given a set $S$, is it possibly for Alice or Bob to find a winning strategy so that they always win?
Suppose $S$ is countable. Then we can enumerate $S = \{s_1,s_2,s_3,...\}$. In this case, Bob can always win (I'll let you think about why he can always find a winning strategy! It's a little tricky but should be do-able with a little familliartiy with countability).
But what if $S = [a,b]$? Well then clearly Alice wins, because $a' \in(a,b) \subset [a,b]$.
So $[a,b]$ cannot be countable!