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Penrhyndeudraeth to Blaenau Ffestiniog. Less than 10 miles by road. Fastest journey by National Rail is 6 hours 59 mins. Only three trains needed though.
How about Exmouth to Starcross? 1.5 miles, 44 mins by train.
Yeovil Junction to Yeovil Pen Mill. 1.4 miles as the crow flies: 2hrs 50 mins by rail via Salisbury and Westbury or 2hrs 40 mins via Exeter and Castle Cary.
I nominate the 1729 Gunnislake - Liskeard which takes 22 minutes to get from St Budeaux Victoria Road to St Budeaux Ferry Road which is less than 100 yards.