I don't have SB account with SBI but have PPF account in Gujarat. Can I operate this account from Maharashtra

If you opened the PPF with SBi in Maharashtra, then you need to operate it from there. In case you are moving, you can give an application & your passbook to whichever new branch you want this transferred to & they will do the needful. In my case, it took a good 2 months.
I am thinking of opening up a savings account with SBI so that I can use my PPF account online.

Yes. SBI has no link with PPF.

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