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Compiling your PSPSDK+Toolchain on Ubuntu:

Open a terminal.
Become root.
sudo su
Install required packages
sudo apt-get install build-essential autoconf automake bison \
flex libncurses5-dev libreadline-dev libusb-dev texinfo libgmp3-dev \
libmpfr-dev
Download the latest toolchain.
svn co svn://svn.ps2dev.org/psp/trunk/psptoolchain
Setup the environment.
gedit ~/.bashrc
Add the following lines at the end of file, save then close.
export PSPDEV=”/usr/local/pspdev”
export PSPSDK=”$PSPDEV/psp/sdk”
export PATH=”$PATH:$PSPDEV/bin:$PSPSDK/bin”
Load environment changes.
source ~/.bashrc
Now for the long part, build the toolchain and sdk.
sudo ./toolchain-sudo.sh
The compile takes 30 mins to 4 hours, depending on the machine. My rig is an AthlonXP 1800+, and only took less than 2 hours.

Now you can start programming your PSP, the open source way. Enjoy XD.

Edit[2009/07/01]:
Added libmpfr-dev to required install package. This should fix the problem with missing mpfr.h

Edit[2008/11/21]:
Added libgmp3-dev on the required packages. And there seems to be a problem with the gcc in the latest version of Ubuntu(Intrepid Ibex). Here’s a workaround:

Install GCC 4.2
sudo apt-get install gcc-4.2
Modify toolchain-sudo.sh, adding following right before “export PSPDEV=/usr/local/pspdev”
export CC=/usr/bin/gcc-4.2