Bridges into Work 2, backed by £5.4m EU cash, will be on offer to over-25s in Blaenau Gwent, Bridgend, Caerphilly, Merthyr Tydfil and Torfaen.
It aims to find jobs for at least 400 people and qualifications for 1,000.
Finance Minister Jane Hutt said the scheme will "help remove the barriers that prevent people getting into work".
The three-year project includes advice on job searching, presentation skills and CV writing, plus opportunities to take qualifications or vocational training.
Extra support is offered to people whose ability to work is affected by health, childcare or transport issues.
The first phase of Bridges into Work, from 2009 to 2015, cost £27m and helped almost 4,000 people find work and more than 14,000 get new qualifications.
The scheme is run by Torfaen council on behalf of five local authorities, with Bridgend replacing Rhondda Cynon Taf in the latest phase.
Two thousand unemployed people in the south Wales valleys will be offered training and mentoring in a new £7m project to get them into work.