The line-up includes lawyers who helped him win a stunning court ruling that overturned the 2019 victory of his predecessor Peter Mutharika because of fraud claims, and called for a vote re-run.
Chakwera, a former evangelist preacher, won the replay with almost 59 percent of the vote and was sworn in on Sunday, vowing to maintain unity in the southern African country.
The result was hailed by African leaders as a model for a peaceful handover of power in the region.
Among Chakwera's top appointments, the crucial post of finance minister was given to seasoned company executive Felix Mlusu, the former managing director of a Malawian multinational financial holding company.
Modecai Msiska, Chakwera's lead lawyer in the election court case, was named justice and constitutional affairs minister, while another lawyer involved, Chikosa Silungwe, was named attorney general.
Saulos Chilima, who was sworn in as vice president on Sunday, will also take the post of minister of economic planning and development and public sector reforms.
Some 6.8 million Malawians had returned to the polls Tuesday after the Constitutional Court found the May 2019 election had been marred by "grave" and "widespread irregularities" -- including the use of correction fluid to tamper with result sheets.
Chakwera leads Malawi's oldest party, the Malawi Congress Party (MCP), which previously ruled from 1964 to 1994 under Hastings Banda's one-party rule.
Malawi is only the second sub-Saharan African country to have presidential poll results overturned in court, after Kenya in 2017.
It is also the first time in the region that a vote re-run has led to the defeat of an incumbent leader.