Theoretical pi-based stream cipher
The problem with this approach is that it literally gains you nothing. In order to choose a random subsequence of a needed length from $\pi$, you need to generate a cryptographically random number of at least the same length of the desired key to use as the offset. But then you may as well just use that number as your secret key.

Other than that, yes, it's exactly the same as a one-time pad. Just with a silly and pointless key derivation protocol which cannot mathematically increase the security of the system, but could conceivably weaken it.

Edit: As Thomas points out in the comments, the distribution of digits of $\pi$ are not random, and so this mechanism of key generation actually discards a significant amount of entropy that had been generated while choosing a random offset.