But local favourite Janez Brajkovic stuck with the Colnago-CSF rider as he took victory on stage three and is in striking distance to snatch the win on Sunday.
Pozzovivo and Brajkovic were far too strong for the rest of the field on the tough stage, losing the peloton during the first category climb of Soriska Planina.
“After the second ascent to Soriska, I noticed the others were weakening so I started to dictate the pace and when Pozzovivo came with me, we continued to the end,” Brajkovic said afterwards.
The pair set a relentless pace from the base of the mountain, opening up a 24 second gap over the peloton by the time they had reached the summit.
The duo then extended their lead during the descent, enjoying a 1:53m advantage over Kristjan Koren and Daniele Ratto by the time they crossed the line.
Pozzovivo eased over the line ahead of Brajkovic in the two-man sprint at the end of the stage to take the yellow jersey but is realistic about his chances of wrapping up the win.
“It was very difficult for me because the last climb was 40km from the finish,” said Pozzovivo. “I worked with Jani and we made it to the finish.
“I got the win here, but tomorrow in the time trial, I won’t have much of a chance against him.”
1 Domenico Pozzovivo (Ita) Colnago - CSF Inox
2 Janez Brajkovic (Slo) Astana Pro Team
3 Kristijan Koren (Slo) Liquigas-Cannondale
4 Daniele Ratto (Ita) Liquigas-Cannondale
5 Danilo Di Luca (Ita) Acqua & Sapone
6 Francesco Failli (Ita) Farnese Vini - Selle Italia
7 Tomaž Nose (Slo) Adria Mobil
8 Matteo Rabottini (Ita) Farnese Vini - Selle Italia
9 Winner Anacona Gomez (Col) Lampre - ISD
10 Kevin Seeldraeyers (Bel) Astana Pro Team
11 Bruno Pires (Por) Team Saxo Bank
12 Dominik Nerz (Ger) Liquigas-Cannondale
13 Jure Golcer (Slo) Tirol Cycling Team
14 Jan Polanc (Slo) Radenska
15 Francesco Reda (Ita) Acqua & Sapone
16 Mads Christensen (Den) Team Saxo Bank
17 Vladimir Miholjevic (Cro) Acqua & Sapone
18 Alessandro Bisolti (Ita) Team Idea
19 Damiano Caruso (Ita) Liquigas-Cannondale
20 Sander Armee (Bel) Topsport Vlaanderen - Mercator