Moores, the first man to twice be appointed England coach, replaced Andy Flower after the former Zimbabwe batsman stood down following the team's 5-0 Ashes thrashing in Australia.
In a two-year spell from 2007 to 2009, the 51-year-old Moores led England in seven Test series, starting with a 3-0 win over West Indies, after replacing Duncan Fletcher.
However, he was forced out in 2009 following a rift with Kevin Pietersen that cost the star batsman the England captaincy, although the ECB ended Pietersen's international career after the recent Ashes debacle.
Moores joined Lancashire in February 2009, having previously guided Sussex to the County Championship title in 2003.
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Lancashire had not won the championship outright since 1934 but their long wait ended in 2011.
In an ECB statement, Moores said: "I am very excited about the prospect of returning to a role I have done before and to building a strong relationship with (captain) Alastair Cook and the rest of the players and staff.
ECB managing director Paul Downton added: "Peter has a great reputation around the world as an outstanding coach and he will return to the role as England head coach with a great deal more experience and understanding of the challenges that the role presents.