If a unit elects to perform a Stand & Shoot reaction it fires any missile weapons it has against the charging foe. A Stand and Shoot reaction can only be declared if the unit has missile weapons of some kind.
A Stand & Shoot reaction can only be declared if the range to the enemy is greater than the charging unit's Move characteristic.
If a Stand & Shoot charge reaction is declared, the unit makes a normal, although out of sequence, shooting attack against the charging unit (see the Shooting chapter for more details on shooting attacks). Once the shooting attack, and any Panic test caused by it (detailed in the Panic chapter), have been resolved, the unit is treated as having declared a Hold reaction.
A Stand & Shoot reaction can even be declared against an enemy unit that starts its charge outside the firing unit's maximum range – the shooting is resolved normally before the charging unit moves. It is always assumed the enemy is just within maximum range of the shooting unit's shortest-ranged weapon, even if the charge fails for whatever reason.
In most cases, there is no downside to a Stand & Shoot over simply holding.