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I was on an 8pm train from newbury to paddington last night as it happens. I got the reservation by messaging them on twitter. I just said the exact train I was on and then the customer service rep sent back an image from their booking system. I go on GWR pretty regularly and cant remember last time I was asked for a reservation. That said, with there only being 4 spaces because its shit (I actually also work at the DfT) it's probably worth doing it.
Aye on the app. I bailed out last night riding back from Bristol, no ticket office open at Newbury, no bike reservation option on the ticket machine, couldn't get through on the phone.
It's just weird the app lets you reserve a space but you get nothing to show for it, luckily I didn't have to debate this with the guard as loads of space at 7pm on a Sunday in November..