Anne Houston, who recently retired as chief executive of the charity Children 1st, has backed a Yes vote in September's referendum.
She argued too many people in Scotland are living in poverty and attacked "retrograde" Westminster welfare reforms which she said were hitting people in low-paid employment and those with disabilities.
Ms Houston said: "Vulnerable families and their children are being made more vulnerable.
"It is unacceptable that one in every five of Scotland's children is living in poverty, a rising figure.
"For me the decision is about the difference independence would make to our control over the things that matter most to us. Many of our priorities are patently different from those driven by Westminster.
"I am in no doubt that by taking control of our own decisions and meeting our own priorities with independence we have a much better chance of giving our children the protection and support they deserve."
Ms Houston stressed her lack of party affiliation and said her decision to back independence had been shaped by 40 years of personal experience in child protection.
She said: "People often say children are our future and that is true, but they deserve more.
"We should value our children - and in a small country like this with our own choices we can do that better.
"This is about a positive vote for our future and is not about voting for any particular political party - that comes later.
"In an independent Scotland we can together identify the fundamental principles that will address what we care about and believe in - our aspirations for our country. That's why I'll be voting Yes on September 18."