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If I take the Wild Talent feat (from UA 2020: Psionic Options Revisited, DM approved) and improve my Charisma, this allows me to do the following:

You awaken to your psionic potential, which enhances your mind or body. Increase one ability score of your choice by 1, to a maximum of 20, to represent this enhancement.

You also harbor a wellspring of psionic power within yourself, an energy that ebbs and flows as you channel it in various ways. This power is represented by your Psionic Talent die, the starting size of which is a d6.

[...]

Psi-Guided Strike. Once on each of your turns when you hit with an attack roll that uses the ability increased by this feat, you can roll your Psionic Talent die after you make the damage roll and then replace one of the damage dice with the number rolled on the Psionic Talent die.

Chaos Bolt requires an attack roll based on my spellcasting modifier (I am a Sorcerer, using Charisma) so it should benefit from Psi-Guided Strike.

Per the description of the Chaos Bolt spell:

You hurl an undulating, warbling mass of chaotic energy at one creature in range. Make a ranged spell attack against the target. On a hit, the target takes 2d8 + 1d6 damage. Choose one of the d8s. The number rolled on that die determines the attack's damage type, as shown below.

(Cue table that isn't relevant here. Here comes the section in question:)

If you roll the same number on both d8s, the chaotic energy leaps from the target to a different creature of your choice within 30 feet of it. Make a new attack roll against the new target, and make a new damage roll, which could cause the chaotic energy to leap again.

Suppose I cast Chaos Bolt, and roll a 2 and a 6 on my 2d8 for the spell's damage. If I then choose to use my Psi-Guided Strike and replace my rolled 2 with a d6, I then roll a 6. Now, the damage rolls would be 6 (from a d8), and a 6 (from a d6, which replaced the other d8). The last d6 technically still adds to the damage of the spell, but it doesn't affect the behavior in question here.

Would Chaos Bolt then activate its secondary ability and leap to another target, as if I had rolled the same number on both d8s?

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You have to roll the same number on both d8

The text of the spell says:

If you roll the same number on both d8s, the chaotic energy leaps from the target to a different creature of your choice within 30 feet of it

Replacing the result of a d8 roll with that of a d6 roll is not rolling the same number on both d8s. The condition only cares about what you rolled on these d8, not on what the numerical outcome is or if you replaced it with something.

However, if you would roll a 2 on both d8s, fulfilling the criterion, you then could replace one of the d8 with your d6 and reroll damage. Even if you then roll a 6 on your d6, causing more damage, the condition that you rolled the same number on both d8 is still true, and you can have the chaos bolt jump to another target.

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    \$\begingroup\$ Another point of interest concerning this : RAW you don't even replace the d8 with a d6, but only "with the number rolled on the Psionic Talent die". So a strict reading makes it so that even if you somehow rolled a d8 Psionic Talent die, you would only replace the damage value, not the die roll itself. \$\endgroup\$
    – Matthieu
    Commented Jan 23, 2023 at 7:50

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