Pro racers can tell the diff,most mere mortals cannot. Shimano trickles their technology down,so today's 105 is better than 5 yr old Ultegra. If two bikes are close,say within $100,of each other in price,and one's 105 and the other Ultegra,then the Ultegra bike might be a better buy(if they didn't lower the other components). But I wouldn't spend $350 or more to get Ultegra unless there were alot of other upgrades as well.
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C'dale BBU('05 and '09)/Super Six/Hooligan8and 3,Kona Dew Deluxe,Novara Buzz/Safari,Surly Big Dummy,Marin Pt Reyes,Giant Defy 1,Schwinn DBX SuperSport,Brompton S6L/S2E-X/M6L-X/S12 T Line