Bigger but with a really nice centre and spectacular mountain surround is Bozen / Bolzano about 3¼ hours by train.
Personally I'd go for a two centre stay rather than rush a day trip from Venice.
Also, note that the real Dolomites, the region called Alto Aldige in Italian is officially bi-lingual and in practise German speaking so everywhere has two place names, starting with Süd Tirol for the region. It's a long story......