You'd have plenty of time taking the train - not sure exactly what time they start, but not far off 6am. I'll know after next week when I'm in Sitges again and can check timetables.
06:50 bus arrives Aeroport at 07:20
07:40 bus arrives Aeroport at 08;10
Thank you for your reply
The timetable for October doesn't seem to be available yet. At the moment the train leaves at 5.45am and then roughly every half hour after that. Journey time is about 45 mins.
Timetable link is here for you to check nearer the time (Source = Sitges..........Destination = Aeroport)
If you are 6 people you can consider booking a private taxi with this company, which is very reliable and normally have good prices www.suntransfers.com they also have a toll free number and you can make a price simulation in their website.
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