There are several tax breaks for college tuition payments: an above-the-line deduction (this break expired at the end of 2013 but likely will be extended for 2014), education tax credits, an exclusion for interest on U.S. savings bonds that you redeem, and penalty-free withdrawals from IRAs. At tax time, review all of the available options (there are different income limits and other rules to consider) before making a choice of which break to use.
For calendar year 2007, taxpayers covered by an HDHP may contribute up to the lesser of the annual deductible or $2,850 ($5,650 for family coverage).