If your sound file have a format other than .ogg, you can simply convert it using any program (Mobile Media Converter) or simply use some command line utilities for media conversion. Here are the instructions you need to follow:
1. Once your custom sound is ready, rename it to the following:
desktop-login.ogg
2. Open now the terminal and run this command to access the Ubuntu sound folder:
gksudo nautilus /usr/share/sounds/ubuntu/stereo
3. In this folder cut the default Ubuntu startup sound (desktop-login.ogg) and paste it elswhere so that you can restore it in the future. Now copy and paste your custom sound in the same folder:
4. Close the folder and reboot to test your new startup sound.
Enjoy!

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