The probe was ordered by the police watchdog after concern over the stop of the athlete, then 27, and her partner Ricardo dos Santos in Maida Vale in July 2020.
The couple accused the force of “racial profiling” when they were handcuffed and separated from their three-month-old son during the stop.
Mr dos Santos was searched for weapons and for drugs and Ms Williams for weapons.
Acting Police Sergeant Rachel Simpson and PCs Allan Casey, Jonathan Clapham, Michael Bond, and Sam Franks are to face misconduct hearings from September 18 onwards over the stop.
All five face allegations that they breached police standards over equality and diversity, while Acting PS Simpson, PCs Clapham, Bond and Franks are accused of breaching standards over use of force and respect.
PCs Casey, Clapham, Bond and Franks also face allegations over the accuracy of their account of the stop.
Gross misconduct is the most serious disciplinary charge the officers can face and, if proven, they could be sacked.
In a previous statement, the couple welcomed the misconduct hearing.
Ms Williams said she hoped the hearings open “the door for the Met to start being more honest and reflective about the culture of racism which is undoubtedly still a reality within the organisation.”
Mr dos Santos added: “This has been a long journey, and one which has not been easy.
“This sheds a light on how difficult it is to ensure the police are held responsible for their failings.”
The Met’s internal Directorate of Professional Standards carried out two reviews, which found no misconduct by any officers, before misconduct hearings were ordered by the police watchdog.
The then Met commissioner, Cressida Dick, claimed that “any officer worth their salt would have stopped that car” and that she did not “personally accept” footage of the stop “reveals racism”.
However, senior officers in the force have previously apologised for “the distress that this incident clearly caused Ms Williams and Mr dos Santos.”