Phil Ward stepped down from the top job at Heston Community School , which he has held since 2005, at the end of the summer term.
He told parents he was leaving to spend more time with his family.
Former deputy headteacher Ranjit Berdesha has been promoted to acting head of the school, where he has worked for the last 15 years.
Governors at the school, in Heston Road, Heston , thanked Mr Ward for his "hard work and dedication", and said he would be "sorely missed".
Writing to parents, they said Mr Berdesha would be able to draw upon his "wealth of knowledge and experience" to provide the leadership needed for the school to "flourish".
In his letter announcing his resignation to parents, Mr Ward described the decision to step down as a "very difficult" one to make.
"Having always put Heston Community School and the students we serve first and at the heart of every decision I have made over the years, I feel that the time has come to devote more time to my wife and family who have made so many sacrifices to support me so patiently and loyally throughout my headship," he wrote.
He described the school as a "very special place" and said it had been a "privilege" to work there.
Heston Community School was recently praised by rugby legend Jason Leonard for helping the sport break new boundaries and flourish at state schools.
It was also one of five schools in the borough this year to make the top 100 schools nationally for various achievements.