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I just did the same thing myself! I've been riding my Trek 8000 mtb with slicks on all the country roads, but wanted something more.
In trying to figure out what road bike to buy, I asked myself first what I wanted most in a bike. And my answer was one that I would not be replacing in a couple of years.
That lead me directly to the Trek 4.5 Madone. And I can say with a full and happy heart that I choose wisely and love, love, love this bike. No regrets. I would also say if you can do it, go for it.
And absolutely positively get a good fitting. Even a great bike won't make you happy if it's not the right fit for you.
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I went from a mountainy-hybrid to a Trek Madone 4.5 and I love love love it. I've put over 600 miles on it since I got it in July. It's a perfect fit.
I did replace the saddle though, only b/c the stock saddle was too soft. I bought a firmer version of the stock saddle, same size/style pretty much, and it is a perfect fit.