Florence to Munich

The Deutsche Bahn has pretty frequent departures taking about 7-1/2 to 8 hours.

You didn't specify a date so I just chose a random March weekday. For that particular day Skyscanner shows that only Air Dolomiti has non-stop flights. Results for a different date might offer more options. Most of the one-stop flights involve connections and will take longer than the train. You might also check for flights out of Pisa.

For both air and rail the fare will vary with how far in advance you buy the ticket. The fare differences can be really substantial, depending on your timing.

The train makes a beautiful trip: crossing the Dolomites.

Eurail blog
Just a quick Google and now I want to make that trip.