Both Vicenza ans Padua are worth a visit,
That's true, going from Venice to Milano is really short, it doesn't need an overnight stop at all. You think about that to see another place, right? A stop on the Garda Lake is a good idea, some nice towns are Desenzano, Sirmione or Perschiera just to name few.
Or, if you want to change your way and don't go straight to Milano, you can even consider Bologna which is at a reasonable distance from both Venice and Milano.
We did Verona for one night between Venice to Milano and the old Roman buldings were a nice contrast with the other two cities.
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