Murcia is the name for the city and also the region in southern Spain.
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West towards Granada, Almería or East towards Alicante
There is a petrol station called Santomera Repsol on the A-7 which is the last "big-one" heading west. Afterwards you only have like millions of small ones and often away from the motorway. It is not a AP anymore, only an A-road.
Take bus number 36 towards Santomera/La Matanza (there are only 3 buses per day going further than Santomera, 10:30, 17:30 and ..., otherwise you have to walk like 2-3 km north from Santomera on the MU-414). Ask the driver to drop you off at the roundabout directly after crossing under the A-7. Take the small road on that roundabout eastwards and choose which side you want to hitchhike (there is a little tunnel after like 200 m). The petrol station is like a 20-minute walk away.
PS: By the small road it means the one that is initially not paved and leads to the left becoming a paved road after 100 meters or so.
Tested yesterday 25.03.2010 - worked like a charm. I waited around 30 minutes including the coffee I hadat the gas station. (location on map)
I tried to hitch hike from this petrol station on the 27. 01. 2012. Even if I took the wrong bus and I had to walk 1 and half an hour, it was easy to find and this is a big petrol station. I was incredibly lucky because the first people who I asked took me on the whole way to Malaga :) I had a very good experience to hitch hike from there :)
Re-tested yesterday on the 29.08.2016! The easiest ride we got in Spain, even though we are a couple with a medium-large dog, we still got a ride in ten minutes literally by sitting down eating with a sign above our backpacks! The sign said Alicante, but we went all the way to Valencia! Lucky spot!
bailamooos re-tested this on 24.08.2016 with great success. I arrived here at 10pm from Alicante heading south/west, pitched my tent behind the gas station for the night, woke up in the morning and hitched a ride within 45 minutes all the way to Almeria.
Tested Oct 2016 and there must have been some changes in bus schedules because there is no bus from Murcia to Santomera/La Matanza. The farthest you can go by bus is to Santomera. I asked various bus drivers and the lady in the ticket office and everywhere the answer was the same - no more buses to Santomera/La Matanza. For us, hitchhikers, it means a longer walk to the petrol station... So there is just a bus going to Santomera. It takes ~40 min from Murcia central bus station to Santomera and costs 2,05 €. Get out on the last bus stop in Santomera and be prepared for ~3km walk till autovia plus ~1km on autovia itself until you reach the gas station (there's no other way, you basically have to walk a bit on the autovia in order to get to the spot)... Despite difficulties to get there the petrol station is quite busy and it's fairly easy to catch a long ride there.
West towards Granada, Almería
Take bus number 44D towards Alcantarilla that is actually going further on the N-340a (only like 3 a day, otherwise you have to walk from Alcantarilla, bus number 44). There is a petrol station on the N-340a where you have to get off and head towards the A-7 (bus stop 'Hotel la Paz'). Right after the bridge over the A-7 you have the petrol station and camping site where you can get east or west, but west should work better. It can take a little bit for there are not too many cars stopping. (location on map)
There are no gates in Murcia main station so you can just get into any train and try your luck. (information from February 2021)