The game had finished 1-1 in normal time, Aggie Beever-Jones netting her first goal for the Blues after Natasha Harding had given the Villans the lead shortly after half time.
And with the game in deadlock, Natalie Bjorn netted the winning spot-kick following Ramsey keeping Anna Patten and Laura Blinkilde-Brown out from 12 yards.
Brian Sorensen utilised the squad’s strength in depth and made eight changes from the team that downed Villa in the WSL on Saturday. The Toffees were in confident mood, moving the ball about well as the personnel changes looked to make their mark.
But it was Ramsey who was by far the busier of the ‘keepers, first denying former Blue Kenza Dali and Villa captain Rachel Corsie, before completing a trio of stops when she prevented another former Toffee, Chantelle Boye-Hlorkah, by parrying her rasping effort.
Elise Stenevik did well to create the only real chance for the hosts. Evading the Villa defender brilliantly, her effort was wide of the target.
Ramsey continued to be the hero as the half drew to a close - something she would later repeat in the shootout. Corsie’s close-range effort seemed destined for the back of the net, but the Blues’ custodian brilliantly tipped over to keep the scores level at the break.
She could do little about Villa’s opening shortly after the restart, Harding finally getting the better of Ramsey with a composed effort.
Sorensen looked to his bench and the introduction of Bjorn and Jess Park, the latter in particular making an instant impact. The Manchester City loanee collected the ball before feeding Beever-Jones, who rounded the Villa goalkeeper to restore parity.
Park’s introduction tipped the game in favour of the Blues, her fine pass then picked out Aurora Galli, but the Italian failed to keep her effort down.
And with the two sides unable to find a winner, Ramsey ensured the headlines would be about her and the bonus point would be staying on Merseyside.
Lucy Graham, Stenevik and Hanna Bennison all netted from the spot to put Everton in control of the shootout, with the Blues’ stopper denied Patten and Blinkilde-Brown to give Björn the opportunity to win it for the Blues.
And she made no mistake from 12 yards, giving the Blues a win in the opening Continental Cup game and condemning Villa to a second defeat to Everton in four days.
Brian’s verdict on tonight’s shootout win: pic.twitter.com/ggCUmHGG6F— Everton Women (@EvertonWomen) October 26, 2022
Sorensen’s side won’t have much time to celebrate, a visit from high-flying Manchester United is next up on Sunday, with the Toffees looking for a fourth WSL win and to inflict a first league defeat on the Red Devils.