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There is a frequent bus serice from La Spezia to Portovenere but I had some difficulty finding the bus stop near the station when I used it last year. It only stops outside the station on a Sunday! During the week it is some distance away in one of the main shopping streets. The directions given in the above posting should be very useful to you. I found Portovenere a delightful place to viisit. Best of luck finding the bus stop!
As I recall, La Spezia station has a tourist office and a national park office. Either would be able to tell you the way to the bus.
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