The Reds were supposedly keen on a move for the winger back in January but opted to bide their time and wait until the summer.
Mertens has spent three years at Napoli since signing from PSV Eindhoven but spent the majority of his time utilised as a substitute.
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A potential fee hasn't yet been mentioned, but with only two years remaining on his current contract and first-team action hard to come by in Serie A, a move could well transpire.
However, following his hat-trick against Bologna last night, rumours also suggest that Napoli are hoping to tie down the Belgian down to a new deal.
Mertens' arrival would likely be a welcome one at Anfield given Liverpool's dearth of out-and-out wingers, with his pace and athleticism assets that Liverpool could do with in the wide areas.
Manager Jurgen Klopp's preferred formation on Merseyside - and at Borussia Dortmund - is 4-2-3-1, with quick and technical players on the flanks. Marco Reus and Pierre-Emerick Aubameyang filled those roles at the Westfalenstadion, but Klopp is yet to find the perfect combination at Liverpool.
The German's philosophy also relies largely upon defending from the front, which Mertens would be able to provide. His build and energy is well suited to the Premier League whilst his experience in European football would be an important addition to a side short of it.
Whether rumours linking Mertens to Anfield materialise remains to be seen, yet the pulling power of Klopp and the possibility of offering Champions League football through winning the Europa League suggests a busy summer is imminent for Liverpool.