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Polearm Master allows a PC to make an opportunity attack when an enemy enters within reach.

With the Brace manoeuvre, you can use a reaction to make an attack, expending a superiority die.

BRACE When a creature you can see moves into the reach you have with the melee weapon you're wielding, you can use your reaction to expend one superiority die and make one attack against the creature, using that weapon. If the attack hits, add the superiority die to the weapon's damage roll. Tasha’s Cauldron p.42

Do these features stack, meaning - can they occur simultaneously or on the same turn? What would be a way to make use of both of these character abilities?

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    \$\begingroup\$ What do you mean by "stack" in this context? \$\endgroup\$ Jul 9 at 0:35
  • \$\begingroup\$ @RyanC.Thompson i’ve updated to clarify \$\endgroup\$ Jul 9 at 1:30
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No, they do not stack because you can only take one reaction per round so it's either/or, not both.

Page 190 of the PHB states:

Reactions

[...] When you take a reaction, you can't take another one until the start of your next turn.

Both Opportunity Attacks and the Brace Maneuver allow you to use your reaction but they are both separate instances. You can use your reaction to make an opportunity attack or you can use your reaction for the Brace Maneuver, not both.

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    \$\begingroup\$ A cavalier with its capstone ability can take a special reaction for an opportunity attack every turn in combat, but not the same turn as it uses its reaction. Which still means you can't do both on the same turn \$\endgroup\$
    – Tiger Guy
    Jul 9 at 4:52
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    \$\begingroup\$ I think this is a good answer, but there are a couple of edge cases that spring to mind: 1. A 17th level Thief gets an extra turn on the first round, so could use two reactions in a round. (Although the answer to the original question is still "no", because it doesn't enable you to use both on the same turn.) 2. The optional rule in the DMG - mark - allows you to make an opportunity attack without expending a reaction. If playing with this rule, you could use both an opportunity attack and brace on the same turn. \$\endgroup\$
    – F1000003
    Jul 9 at 9:37
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Action options - Mark in the DMG p 271 might allow you to take two reactions (sort of). Depending on the DM.

When a creature makes a melee attack, it can also mark its target. Until the end of the attacker's next turn, any opportunity attack it makes against the marked target has advantage.

The opportunity attack doesn't expend the attacker's reaction, but the attacker can't make the attack if anything, such as the incapacitated condition or the shocking grasp spell, is preventing it from taking reactions. The attacker is limited to one opportunity attack per turn."

So in your case Brace uses the reaction and you mark your target, then you get an attack of opportunity with your mark.

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