"Annual leave begins to build up (accrue) as soon as a worker starts their job". - HMRC
Holiday entitlement will be set out in the Contract of Employment. This will normally always be based on the model, or now, template contracts and will provide a higher entitlement than the statutory minimum.
Every employee is entitled to take annual leave, regardless of how many hours they work. An easy way to calculate an employee's statutory annual leave is to use HMRC's annual leave calculator which can be found here using this link to the government page called calculate holiday entitlement.
If you are unsure on some of the particulars of employee annual leave, here is a link to the government page called holiday entitlement.
It is important to know that this does also include those on a zero hours contract, however, annual leave should be calculated and paid to the individual on a monthly basis in this case.
At the beginning of each leave year (for example 1st April to 31st March) I recommend carrying out the following steps:
calculate an employee's annual leave (using the HMRC annual leave calculator if applicable).
This total is including bank holidays so deduct the bank holidays during this period from the employee's annual leave amount.
What you have left is the employee's annual leave to take as they wish. Then record and deduct any annual leave dates requested, or as you go along throughout the year.
If your employee exceeds their annual leave amount, you are entitled to permit 'unpaid leave' and in this case please let your payroll officer know to deduct this from the next pay run.