Yes, you can send a CHAPS payment by contacting customer services. You must contact customer services on a working day, between 9am and 3pm for the payment to be sent on the same working day. 

Often it is easier to send payments via Faster Payments. If you contact customer services, you can send a maximum of £500,000 via Faster Payments in a day. The upper limit for a single Faster Payment is £250,000

From 4th November, sending a CHAPS payment will cost £20 per payment. Faster Payments will continue to be free.