Ineos Grenadiers rider Tarling finished the 13.7km course of the Albanian capital in 16 minutes and seven seconds - finishing one second ahead of Primoz Roglic, with Jay Vine three adrift as he took third for UAE Team Emirates.
Red Bull-Bora-Hansgrohe's Roglic, the 2023 Giro champion, takes the overall Maglia Rosa leader's jersey, with stage-one winner Mads Pedersen a further second behind in the general classification standings.
Tarling faced an anxious wait as 58 riders tried to beat his time before his first Grand Tour stage victory was confirmed - the 21-year-old Welshman also becoming the youngest time trial winner at the Giro.
"I can't believe it. I have been trying [for a long time] - I'm so happy," said Tarling, who is making his debut in the race.
"The wait wasn't nice - I don't want to do it again! It was a long day for 13km and I feared all the big favourites."
Sunday's third stage of the Giro will also be in Albania, across a 160km stage which starts and ends on the coast in Vlore, following a climb of the Llogara Pass.
The race will then resume back in Puglia on Tuesday.
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