The Domane has a slightly longer wheelbase, relaxed geometry and higher head tube, not to mention the slight rear suspension. It takes the edge off in that it doesn't require quite the attention that the Madone does - mainly due to its longer wheelbase and more relaxed front end geometry. It makes it a bit easier to chat with others riding beside you, to not worry so much on gravel or cobblestone like surfaces, and even snap a few pictures while underway. This doesn't mean its a only a cruiser though, as its got excellent lateral and BB stiffness for spirited acceleration and general handling performance.
The Madone is a race bike designed for smoother or less rough pavement, and quick turns when you're surrounded by other cyclists and jockying for position. It can turn a tighter radius than the Domane. A good race bike will feel almost twitchy or nervous in the front end at times. It wants to be driven into corners and accelerate out. The Madone wants its rider to get out of the saddle for sprints and sway the bike back and forth putting the hammer down.
Both bikes can fulfill the purpose of enjoyable cycling as there is plenty of overlap. If you're not going to race, I would recommend the Domane. If you're going to be riding full centuries (100+ miles) the Domane will treat you nicer in that its ride is a little smoother. If you're planning to train for crits and race, go for the Madone. But again, there is lots of overlap and you will likely be happy with either.
I agree with NealH. I am 55 and rode both the Madone and Domane Six bikes. I really liked the get up and go, racy attitude of the Madone. It was super fast, snappy, and a joy to ride. But in the end I ended up with the more comfortable, predictable Domane. I am satisfied I made the correct choice for the type of mid range riding I do. I'm good on flats and decent on hills, too as I like climbing. The Domane is plenty stiff, and lots of fun.
I'll be the devils advocate...I've been on a Madone since my 2008 5.2...put just shy of 20k miles on that bike before a car clipped me and broke the headtube. Picked up a 2010 6 Series Madone and have put almost as many miles on it - mainly rural mountain roads in Northern California/Southern Oregon (general riding and t-shirt centuries).
When the Domane's showed up, I grabbed one from my LBS for a demo/test ride. While very comfortable, too many years on a stiff/snappy Madone has ruined me. Even in my mid 40's as a non-racer, I found I preferred the quicker turning and slightly stiffer Madone. So much so, that I ordered a 7 series to compliment my 6
So for me, it's the Madone over a Domane.
YMMV...as long as you're out riding, that's all that counts. So find what fits you best and buy as much bike as you can afford - you'll appreciate the better components.
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