Michael Woods and Billy Paynter were the goalscoring heroes for Pools as a strong display after the break proved too much for a City side who are still waiting for the first point of the season.
Craig Hignett opted to make five changes for the trip to Devon, as Trevor Carson was restored in goal and Rob Jones, Nicky Featherstone, Lewis Hawkins and Paynter all returned to the starting line-up.
It was a scrappy start to the game at a sun-baked St James’ Park, with both sides struggling to play much of the free-flowing football that the fixture had promised.
A Robbie Simpson free-kick was charged down by the wall, while his strike partner Liam McAlinden almost got the better of Toto Nsiala but the Pools defender recovered well to deflect his shot over the bar.
A McAlinden snapshot was easily held by Trevor Carson as the hosts started to threaten more; Pools were only fleetingly dangerous on the break with Lewis Alessandra the main outlet.
However, just after the half-hour mark City found the breakthrough when a quick throw-in on the left caught Pools out; Ollie Watkins burst in to space on the left of the area and cut the ball back for McAlinden who stroked it low across Carson and in to the bottom corner of the net.
Watkins drove a speculative effort over the bar and Nathan Thomas hit the wall with a free-kick at the other end before Carson got down well to claim a header from Simpson which was destined for the right corner of the net.
Boss Hignett clearly wasn’t happy and made a double change at half-time – the injured Rob Jones gave way to Matthew Bates and Lewis Hawkins was replaced by Padraig Amond.
And the Irishman could have announced his arrival with the leveller inside sixty second of the restart after harrying the defender in to an error but he stabbed his effort agonisingly wide of the post from twelve yards.
However, that attacking menace set the tone for a vastly-improved second half display as Pools dominated possession and created numerous chances.
Carl Magnay’s sweeping diagonal ball was perfect for Thomas to take on his chest and drive in to the box but his drilled shot was well-parried by Olejnik.
That stung City in to a reaction with McAlinden firing a shot just over the bar from the edge of the area before Watkins was denied by a smart save from Carson.
The Grecians came even closer to doubling their lead when Lloyd James clipped a free-kick over the wall but it bounced off the frame of the goal and Pools scrambled it clear.
An error from Nsiala allowed McAlinden away down the left but his dangerous, drilled cross evaded everyone in the box and Pools survived again.
It was only brief respite for the hosts though because Pools were quickly back on the front foot and Nsiala got free at the far post from a Thomas free-kick but couldn’t force it past Olejnik.
Pools’ patience was rewarded on 74 minutes when Michael Woods helped a right-wing throw-in round the corner to Amond who released Alessandra to the byline; he drilled a ball low in to the six-yard area where it popped out to Michael Woods to ram home left-footed.
The 121 travelling fans had hardly stopped celebrating when Pools hit the back of the net again; Magnay sent a ball in from the right, Amond stepped over it and the brilliant Paynter smashed a low shot beyond Olejnik to make it 2-1.
City substitute Conor Riley-Lowe almost carved out an equaliser for the hosts when he lifted a cross in from the left but Watkins glanced his header off target and, with that, City’s last big chance was gone.
Hignett’s men saw out the closing stages with professionalism and, in truth, looked more likely to add a third goal near the end than concede a leveller.
The full-time whistle was greeted with cheers on the pitch and in the terraces as Pools got their season firmly up and running with a first victory to ensure the long journey home was a happy one.
Full Time: Exeter City 1 Pools 2
Booked: Featherstone (52)
Attendance: 3322 (121 Pools)
Exeter City: Olejnik, McCready (Egan 89), Woodman (Jay 86), James, Tillson, Simpson, Watkins, Moore-Taylor, McAlinden (Riley-Lowe 70), Taylor, Sweeney.
Subs Not Used: Ampadu, Pym, Storey
Pools: Carson, Magnay, Nsiala, Jones (Bates 45), Carroll, Featherstone, Woods, Hawkins (Amond 45), Alessandra, Paynter (Oates 86), Thomas.
Subs Not Used: Bartlett, Richards, Deverdics, Laurent.