It seems highly likely the 29-year-old will go as first-choice left-back with England boss Roy Hodgson having to make a decision over whether to opt for the experience of Ashley Cole, for a long time the automatic pick in that position, or give Southampton youngster Luke Shaw a chance.
In Baines and right-back Seamus Coleman, who is the club's joint second-highest scorer this season with six goals, Martinez has two players ideally suited to his brand of football.
"I think the full-back position is the most demanding in world football - you need to be able to defend in a unit, one v one, and full-backs are probably the players who can dislodge defensive set-ups and become vital in your attacking play," said the manager.
"We are blessed with the qualities we have.
"Leighton has been playing really well of late and it was a great opportunity for the England manager to see other options (against Denmark) and we are delighted he was rested and can carry on preparing for the game (on Saturday against Arsenal).
"In the case of Leighton he has been such a consistent performer everyone knows what a player he is developing into and what he can bring.
"When you go into a major tournament experience plays a big part and Leighton is probably in the best moment of his career.
"I think he is in the peak of his career to help the national team and from our point of view to help our club.
"I am excited about the ending of the season with Leighton's form and making sure we are as strong as we can be."
Baines' defensive colleague Phil Jagielka will probably not be fit for Saturday's FA Cup quarter-final at Arsenal, having missed the midweek friendly and last weekend's league win over West Ham, but fellow centre-back Antolin Alcaraz is fit after more injury problems.
"It is very unlikely Phil Jagielka will be involved
If the game was tomorrow he wouldn't be available," added Martinez, who maintains keeping on-loan striker Lacina Traore is still a good idea even through the player could be out for another six weeks with a hamstring problem.
Martinez denies the club made a mistake with the Ivory Coast international, who arrived from Monaco in January with a hamstring problem having also not played since the end of October, who has played just an hour in one appearance.
"We want to work with Monaco and we have the individual programme," said the Toffees boss.
"We've seen the specialist and everything has been organised for the specific training for the next five weeks.
"It is a separate injury but in the same muscle
It is always a concern when that happens, especially when Lacina is the type of footballer he is, a sprinter.
"This time we never rushed him back
When you rush someone back you are working with fatigue and the risk of injury is there but he travelled with the team for a couple of games and then played 60 minutes.
"It has been a difficult time for Lacina but it is nothing he has done wrong.
"I do feel if we can get him fit before the season ends we can see a player desperate to help the team."
Source : PA
Source: PA