So to provide a bit more details:
* In terms of documents we had:
1) Me :
a) Application Form - SET (O)
b) Passport
c) Two photos
d) Bank statement for last 12 months
e) Payslips for last 12 months
2) My wife :
a) Application form - PBS dependent
b) 3 months bank statement to prove the balance
We just had the documents required by the form and that was it
* Our experience on the day
1) Arrived in Croydon Home Office Centre by 8:50am
2) My appointment was 9:30am and my wife's was 10:30am (appointment was made this way because mine was ILR and my wife was dependent PBS on me)
3) At the door, advised the security guy that we are here for PEO. Was then asked to enter a waiting room for PEO. Since the opening hour was not yet, there a number of people waiting
4) Door opened at 9:00am and we queued for airport-looking-like security check
5) Went to the first room and the guy checked our payment form
6) When he confirmed the payment page was completed correctly, we were asked to go to upstair to make payment
7) Made payment by card (forgot to tell my bank that I will be making the large payment but thank God, it went through
Went to the main waiting room at 9:20am. By this time, we had a ticket from the payment booth with our waiting number. We both had only one ticket when we advised the payment booth that our application needs to be assessed together. A lady at the booth checked our entire form, took only 10 minutes and was asked to take a sit and wait to be called.
9) Was called for a Biometric at 9:40am. We went together. Biometric was completed by 10:00am. Very nice person and everything was very easy
10) Was asked to wait in the main waiting area again
11) By this time, the room was getting filled up with people with solicitors, people making payments back and forward
12) Waited a little long time...We were getting hungry and thirsty. There was a cafe but only accept cash.
13) At 10:45am, we were both called to come to present our applications and documents. She was a bit upset that we both only had one ticket number. But when we explained, she went away and came back in 5 minutes and said it is ok and she started assessing mine and my wife's application.
14) We were asked to go back to where we were sitting while she was assessing. She seemed like she knows what she needs to do and was only called once before she approved.
15) After 20 minutes, she called me again and said it is all fine and approved and the BRL card will be sent by post - hurray!
16) She took a bit of rest and called my wife at 11:05am.
17) Waited about another 20-30 minutes and was also called her visa is approved as well! Yahooooo!
18) Packed and came out at 12:00pm after listening all the instructions.
The whole experience was really good. Everyone was nice and easy and people were nice and helpful!
