If you want to open a online account for yourselfyou can do it any time of the day with BT Pay. 

If you want to open a business accountyou can do it 100% online, from anywhere. However, you should know that we can process your online account application Monday to Friday between 09:00 and 19:00. If you send it to us after 19:00, we will be able to process it the next day from 09:00. And if you apply at the weekend, we will deal with it on Monday after 09:00. 😃