401(a) plans are usually offered to a select group of key employees because they're easy to customize. Companies can craft 401(a)s in a way that suits the participants as an added employee benefit. If an employee later leaves the company, they can roll over their 401(a) into another qualified retirement plan, such as a 401(k) or an annuity.
Because 401(k)s and 401(a)s are both retirement plans, you're not meant to withdraw money before turning 59 1/2. If you do, you'll pay a 10% early withdrawal penalty on top of income tax, if your contributions were pre-tax.
If you funded your 401(a) with after-tax contributions, you won't pay taxes when you withdraw your contributions, although you could still owe taxes and penalties on your earnings. There are exceptions to the early withdrawal penalty for things such as major medical expenses and educational expenses, but you still owe taxes on these withdrawals.