Darren Topp has taken the helm at the upmarket retailer whose clothes and shoes sprung to prominence after being worn by the Duchess of Cambridge.
He brings with him Michael Hitchcock, a former financial consultant at BHS who joins LK Bennett as chief financial officer after stints at Beales and Moss Bros.
The retailer said interim chief executive Robert Bensoussan, who took over in 2014, will also stay on as a non-executive director.
LK Bennett, which is owned by private equity group Phoenix, saw group like-for-like sales grow by 5% in the 52 weeks to August 1 last year, while operating profit rose 15% to £3m over the period. Turnover slipped 2% to £93.6m.
Topp said: "We are delighted to be joining the company. LK Bennett is a fantastic business and we look forward to building on and continuing Robert's strategy of developing LK Bennett as a premium accessible luxury brand."
One of Sir Philip Green's former lieutenants, Topp served as chief operating officer at BHS before being promoted to interim chief executive in March last year.
Sources have said Topp's appointment was expected to be confirmed imminently.