In their first fixture since losing the World Cup final, Sarina Wiegman's side came up trumps thanks to Lucy Bronze and Lauren Hemp's headers, but Kirsty Hanson reduced the arrears for Pedro Martinez Losa's side, who subjected England to a barrage of second-half attacks to no avail.
With the bulk of their heroes from Down Under starting at the Stadium of Light - including Lauren James, Mary Earps and Millie Bright - the Lionesses unsurprisingly made the brighter start in their maiden Nations League fixture.
Georgia Stanway attempted a speculative half-volley from range in the 17th minute, which was meat and drink for Lee Gibson, whose opposite number Earps was then forced into a terrific reaction save to keep out Caroline Weir's powerful drive four minutes later.
The Lionesses thought that they had opened their Nations League account in the 25th minute when Rachel Daly met Katie Zelem's corner with a bullet header at the near post, but Chloe Kelly was standing directly in front of Gibson in an offside position and was deemed to have been interfering, leading to referee Maria Ferrieri Caputi chalking the goal off.
A cacophony of boos erupted inside the Stadium of Light, and Scotland almost capitalised on that reprieve in the 28th minute as Hanson sent in an inviting ball for Martha Thomas from the left, but the Tottenham Hotspur attacker could not poke the ball home at the back post on the stretch.
Hanson was afforded ample space to run as Bronze bombed upfield, but the right-back's forays forward would pay dividends with 39 minutes gone, as she held her run and met another inviting delivery from Zelem to pick out the bottom corner with a diving header.
Flaunting their aerial dominance was the key for England, who doubled their lead in the 45th minute with another header, as Daly surged down the right and picked out Hemp to nod home into the top corner.
Wiegman's side would seemingly head into the break with a two-goal lead, but just before the referee's whistle blew, Hanson's tame effort from inside the box found its way into the back of the net via the inside of the post to give Scotland hope.
Buoyed by their timely response, Scotland had the first meaningful chance of the second half with 62 minutes gone, but Thomas's header was far too tame to beat Earps in the centre of the goal.
However, the England number one could only stand and watch alongside her teammates as Hanson's 76th-minute volley sailed over her head, but thankfully for the Lionesses, the ball struck the crossbar and Wiegman's side survived another scare.
The Scotland pressure was incessant, though, and Lisa Evans found Christy Grimshaw inside the D with 85 minutes on the clock, but the AC Milan midfielder's low strike rolled straight into Earps's arms.
A late injury to the effervescent Hanson did Scotland no favours heading into three minutes of added time, during which James also found the back of the net with a header after her initial effort was saved by Gibson, but the Chelsea forward was offside as she charged through.
England occupy second place in the four-team section owing to their opening success, with Belgium leading the way thanks to their identical win over the Netherlands, who the Lionesses meet next Tuesday in Utrecht.