Vladimir's teacher should be Darkin.
Darkin race has very narrow connections with blood magic. Sister, that varus was talking about can be a blood mage who taught Vlad or the last one remaining (fifth darkin).
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I agree it would be pretty cool! I channeled my inner World of Darkness fan to produce this fan theory as soon as the lore came out.
A bit of a problem though: since the Darkin wars were before Noxus, before the Rune wars and in a time generally forgotten by present civilisation, how old does that make Vlad? And what was he doing the entire time empires rose and fell? How would you go about writing a character this fucking ancient?