Having met four times during the regular season, the Capitals and Hurricanes split those matches. The home side came out on top in each game, with the Caps winning 5-4 in overtime when the pair last met a month ago.
The trend of the home team winning came to an end in Tuesday's latest clash. However, the home side did take the lead 3:53 into the second period.
After a battle on the boards, Alexei Protas stole the puck and broke the opposite way. Once he got inside the blue line, he had a go, beating Frederik Andersen to put Washington ahead.
It would take until the midway point of the third period for the Hurricanes to tie things up. This came from an intercepted puck, as Jesperi Kotkaniemi took it from Alexander Alexeyev. The Finn immediately found Logan Stankoven, who converted from close range to tie things up.
The game winner came three minutes into the first overtime period. Jordan Martinook put a shot towards goal, with Jacoob Slavin deflecting it home, fooling Logan Thompson.
The Capitals, who won all three of their home ties in their first round series, find themselves behind going into Thursday's game two.
Later on, the Edmonton Oilers recovered from a two-goal deficit to defeat the Vegas Golden Knights 4-2, as their second round series got underway.