>>20252838Exp Share distributes the exp from killing the mon to all party members. 100% if they participated, 50% if they didn't.
The EVs per kill is distributed based on mon (ex. KO a Zubat, everyone in party gets 1 Speed EV regardless of participation).
When you have a EV affective item on, they proc at the time you receive EXP/EVs.
If you have a Macho Braced Combusken in reserve, and your Talonflame KOs a Zubat, then your Combusken will receive 2 Speed EVs (1 Speed EV * 2). This will only affect the mon holding the Mach Brace, even if Talonflame were to hold it.
tl;dr: Double EVs. EV boosting items do work, and only work for mons that have them equipped.