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iPhone can’t be used as an external hard drive once connected to your computer. In order to add your local movies or songs to your iPhone, things you need to do:
Make sure the file formats are compatible with iPhone. iPhone only accepts videos in MOV, MP4, M4V and some kind of AVI, music in MP3, AAC, AIFF, WAV etc. If not, convert your files to the compatible format first.
Make sure the media file is encrypted or not. If your media files are purchased by yourself from iTunes or shared by others and have been authorized, go to step 3; if not, make it DRM free first.
Sync items from your computer to the iPhone. Take transferring Mac videos to iPhone for example:
iTunes is not available here because it’s a one-way street in transferring. So as to back up your iPhone items to your computer, you can transfer files to Mac OS X Lion via iCloud. To do so, you can back up your iPhone contents to iCloud on your device, then open your Mac to restore contacts, iCal calendars, safari bookmarks and more.
While here I suggest you the most powerful way to transfer iPhone items to your Mac via TunesOver:
Launch the TunesOver and plug your iPhone to Mac. This program will start scanning your iPhone and show your device information on the main interface.
Now go to the "Music" tab or "Movies" tab and select the items you want. Then click the "Export" button on top of the primary window to start transferring. Detailed info: User Guide of TunesOver for Mac.
If you have some photos you wanna add to your new iPhone 5, you can also use iTunes, iPhoto, iCloud and TunesOver to achieve it:
If you used to use a featured phone, an Android phone or an old iPhone, you can also go to Move to iPhone 4S for more info.