Fodorites. . .

I need a little help, I plan on traveling from Friday the 20th of Oct until the 20. I would like to visit Madrid, Tuscanny, Florence, Venice and Rome . . . however I am having trouble planning my schedule. I will fly from Berlin, but logistically should I fly to Italy first and then Spain (or the other way around)?

Madrid doesn't fit, sorry.

If you go to germanwings.com, you will find that discount carrier flies from Stuttgart or better yet Koln/Cologne to Rome, but not from Berlin. So, you could need the first day to just train to Koln and then fly to Rome.(Germanwings also flies to Stuttgart, but connecting Stuttgart to Rome on a discount carrier might be hard to arrange.)

You must figure out how you're going to get to Rome, one way or the other.

Rome 2 nights
train to Venice 2 nights
Florence 3 nights with daytrip to Siena in Tuscany
Rome 2 nights
possible long day getting back to Berlin.

Get the idea? Now, personally ,I think you're better off going to Prague and possibly Vienna from Berlin, given how late the date is and the state of your plans.

10 days isnt long enough to even see two of the places you mentioned in Italy let alone all of them.
Rome, Tuscany, and Florence would be pushing it in that time frame. I would reconsider unless you want it to be a rushed blur.

I would say it's impossible to visit Madrid, Tuscany, Florence, Venice and Rome in 10 days.

Perhaps you can narrow it down to Tuscany and Florence... or maybe Rome, Assisi, Florence, Siena.

Pick 3 max in one country---any more is folly.

The only way I would do this as two countries might be 6 nights Rome and 4 nights Madrid.

Otherwise, I agree with the others--no more that three locations in one country. Each time you relocate to another city, transport and changing hotels will eat up at least half a day.