I don't agree with a lot of the suggestions posted here, particularly those supporting the provision of funds to larger internet-based organizations. Many of these organizations won't put the money to effective use and there's a good chance that it will simply be gobbled up by operating costs or other miscellaneous expenditures.
Ideally you want a lasting return on your investment, so considering education is definitely a priority. Many families who live on either low or no income are not able to afford a decent computer, printer and internet connection and since education begins in the home, this is another area where the money would be well invested. Schools are generally well looked after (in most countries) in terms of their I.T., but schools in smaller countries (such as Samoa and other Island nations), some of which do not enjoy many of the basic schooling supplies-- let alone computers-- would definitely benefit.
Making use of solar in countries which are fortunate enough to have year-round or near year-round sunshine should definitely be considered. Recent advances in IC technology have brought a range of different products to market which are capable of running on very little power. Some examples are VIA's range of small form-factor systems and mobile solutions from companies such as Nvidia (which incorporate a CUDA-powered GPU). Samoa is one such country which would be an excellent candidate for this sort of setup.
Of course, there's no use supplying the technology without having the right people to educate others in how to use it effectively. Funds should be devoted to providing not just training, but the _right_ training to the teachers and other educators who will be assisting students to use this technology. Students need to be able to get the most out of the equipment and software, without having to be put through extensive training and with minimal supervision. The whole experience should place an emphasis on fun, to the point where the students don't even realize they're learning.
Lastly, local investment is key -- create jobs locally, source as much as possible from the local economy and wherever possible, use Open Source operating system and applications... don't throw any more money at Microsoft or any of the other 'Big 3'.