The charity, supported by City firms and financiers, was founded to aid children from under-privileged backgrounds.
Shine stresses that it provides additions to what children are already learning and that most of its literacy and other schemes are held outside the normal school day.
Its creation though appears to suggest that the state system has been under-performing.
But Stephen Shields, the charity's chief executive, said: "We do not want to appear critical of the state education system. With the best will in the world teachers cannot do everything, but we are very respectful of what they do."
The law states that charities cannot provide statutory requirements, but that does not stop schools seeking help.
"The need for our resources is great but there are things we simply cannot help with. Schools won't ask us for help with salaries for example, but it is clear that many are feeling the pinch," Mr Shields added.
Patrons of the charity include Sarah Brown, wife of Chancellor Gordon Brown.