Things have changed
In previes releases of Xcode, you went into Preferences and then to the Downloads tab, and choose to download and install Command Line Tools. In Xcode 5 this have changed. It have been removed, and a new way is intodused. The best part of the new way, is that you don’t even have to install Xcode 5 to get Command Line Tools anymore.
The new way
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Open up an terminal (Terminal.app or iTerm2.app)

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Enter the following command
xcode-select --install.
This will start a wizard that will help you install Command Line Tools in your installation of Mavericks. -
Click on “install” to start the installation wizzard.

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Agree to the
License Agreement
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The Installation will ask you for admin rights and start the installation.

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After the installation is complete, you have Command Line Tools installed.