There was an option in Xcode-3x in preference with a check box to enable or disable the alphabetical listing of methods, as seen in below picture:
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(Xcode3.x option)
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In Xcode-4x they have removed this option.
To list the methods alphabetically press ⌘ and click on the level in the path menu, as in below picture:
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(Xcode4.x, ⌘+click)
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Personally I liked the new feature in Xcode4, as we can list the methods alphabetically or sequentially whenever we want unlike Xcode3 where we had to stick with the option selected in settings tab.
