As both sides continued their build-up to the FIFA World Cup, England youngster Sterling and Ecuador captain Antonio Valencia clashed late on in an incident that saw the duo given their marching orders.
Antonio Valencia took exception to a challenge from Sterling and grabbed the Liverpool winger by the neck, although fortunately for the pair they will be clear to play in the Brazil showpiece.
The flashpoint came at the end of the enthralling friendly that burst to life when Enner Valencia's fourth goal in as many games for his country gave England an early scare.
Wayne Rooney hauled the sides level with a controversial equaliser that appeared to strike Rickie Lambert's arm during the build-up.
Lambert then applied an emphatic finish to a slaloming Ross Barkley run in the opening stages of the second half, only for substitute Michael Arroyo to restore parity with a spectacular 70th-minute strike within a few minutes of coming off the bench.
Alex Oxlade-Chamberlain limped off injured prior to Arroyo's sumptuous leveller having looked bright as the Arsenal midfielder, Lambert and Barkley all gave England manager Roy Hodgson plenty to ponder.
Despite the fact that England started with plenty of attacking intent - Frank Lampard missed the target with a side-footed effort following Lambert's drag back - Hodgson's experimental side were left shell-shocked by Enner Valencia's eighth-minute opener.
Walter Ayovi superbly controlled an aerial ball on Ecuador's left flank before crossing for the forward to sneak in between Chris Smalling and Luke Shaw and steer a firm header beyond Ben Foster, making his first start for his country since November 2010.
Nerves appeared to be getting the better of Foster when he scampered out and failed to win the ball soon after during a swift Ecuador counter, but the West Brom goalkeeper eventually got back on his line and gathered comfortably to collect Carlos Gruezo's weak curling shot.
Lampard let fly from 25 yards to test a sprawling Maximo Banguera after 24 minutes, but England did find the net five minutes later.
Oxlade-Chamberlain sent a delicate chip to the back post as Lambert lurked ominously, although the new Liverpool striker appeared to control the ball with his arm before his close-range backheel rebounded off the post and ricocheted off Banguera to Rooney.
The Manchester United striker, deployed on the left of midfield, duly slotted home his first England goal since October last year and, more significantly, netted a strike that will boost his confidence as he battles to regain full fitness after an injury-blighted end to the season.
Barkley, keen to catch the eye on his first England start, combined brilliantly with Lambert six minutes into the second half to give England the lead.
The Everton youngster nutmegged Jorge Guagua at the start of a jinking run that ended when he rolled the ball into the path of Lambert, who crashed a low effort across Banguera with the outside of his right foot.
Lambert came close to doubling his tally four minutes later after good work from Oxlade-Chamberlain, while at the other end, Enner Valencia somehow managed to hit the post with the goal at his mercy.
Arroyo then made his spectacular impact within a few minutes of his introduction as he moved the ball quickly at his feet to find space ahead of James Milner and Jack Wilshere before rifling into the top-right corner from 25 yards.
Then, with 12 minutes left, substitute Sterling and Valencia clashed in an unsavoury incident that both players will want to move quickly on from with the World Cup looming.
Next up for England is a friendly with Honduras in Florida on Saturday, while Ecuador will head to Brazil in buoyant mood after causing Hodgson's men plenty of problems.