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Welcome!
Yes, you can design your own 'themes' for xoops, and you can customize the layout. Spend some time looking at the default theme and some of the others that are available to see how the 'xoops code' is used to place content in your design.
The layout can be completely up to you, as long as you keep track of which block code you use in the design, and where.
the default set-up is a 4 column set-up, so, when you look at the htmls, you will see how the various colums are defined ie: left column, center left column, center center column (a span of center left and center right), center right column and right column. All of the blocks and modules allow you to place their content in these stated areas, so feel free to move them around in your theme...just pay attention to where you moved them so that you will know which 'column' to place the various blocks in.
Check out the FAQ section....carnuke has put together tons of information (along with input from many xoopsers) on how to create a theme and whats involved.
There is also a Dreamweaver extension set called MyXoopsExtensions that will cut down on some of the 'hand coding' time spent inserting the various XOOPS codes in the html.
Happy Xoopsing!