Edwards replaces Howard Miller at the independent membership body and will work alongside TheCityUK CEO Chris Cummings and chairman Gerry Grimstone.
She joins TheCityUK from Just Retirement, where she was head of public affairs during the group’s initial public offering and listing on the FTSE 250.
At Just Retirement Nicky also launched a campaign to influence public policy on the use of housing equity, and positioned the group as a leading voice on retirement finance and care funding.
She has previously held roles as head of public affairs for The Law Society and the General Social Care Council.
A spokesman for TheCityUK said the role would involve "championing UK financial and related professional services at home and overseas to facilitate economic growth, as well as promoting London and the wider UK as the most competitive location for international financial institutions."
Alongside hiring Edwards, the body has also handed its former CFO Marcus Scott the role of COO.