A superb team goal finished off by Ella Toone was the highlight of a fluid and entertaining first-half display from the European champions, the midfielder arriving in perfect time to slot home Lucy Bronze's cutback and give her side the lead.
Lauren Hemp had a good chance from a Lauren James cross but her header landed into the arms of Brazil goalkeeper Leticia, while James herself had the ball in the back of the net before the break, too, but was denied by the offside flag.
In the end, the Lionesses were made to pay for the missed chances as an uncharacteristic Mary Earps error in stoppage time led to Brazil levelling at the death through Andressa Alves' close-range finish.
Straight to penalties it went and it was there that England secured the win, with Earps making a fine save to deny Tamires, and Chloe Kelly putting away the winning spot-kick in style.
GOAL gives out ratings for an entertaining match below...