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https://reddit.com/link/s41fs8/video/h2o2j0ujlpb81/player

Since Riot routes voicechat through a different program separate from Valorant (you may have noticed missing VC audio when trying to record a video or stream through Discord), you can actually set the volume for voicechat and Valorant ingame audio separately in Windows audio settings. Unfortunately, Windows doesn't have a built-in shortcut to do this, but it is possible using AutoHotKey and a program called SoundVolumeView.

1. Download and install SoundVolumeView here: https://www.majorgeeks.com/files/details/soundvolumeview.html
2. Download and install AutoHotKey: https://www.autohotkey.com/
3. Open SoundVolumeView, make sure Valorant is open (you may need to be ingame/custom match/practice range to ensure it shows all programs)
4. Find "RiotClient", there should be two entries (input and output)
5. Right click the "Direction: Render" entry, and click Create Desktop Shortcut -> Mute/Unmute Switch
6. Go to your desktop and find the shortcut "Mute Switch RiotClient"
7. Right click the shortcut -> Properties, then navigate to the "Shortcut" tab. You'll copy the "Target" entry later.
8. On your desktop (or any folder location), Right Click -> New -> AutoHotKey Script
9. Open the script file in a text editor
10. Clear the contents and enter the script below these steps
11. Replace "" with the Target field in the Properties window of the "Mute Switch" properties window. Make sure to replace the <> arrow brackets.
12. Double-click the script file, it should now be active. You can use the the taskbar at the bottom-right in Windows to find and shutdown the script if for whatever reason you don't want to continue using it.

Note that changes to the script file require restarting the AHK script, they aren't automatically applied if it's already running.

#NoEnv  ; Recommended for performance and compatibility with future AutoHotkey releases.
; #Warn  ; Enable warnings to assist with detecting common errors.
SendMode Input  ; Recommended for new scripts due to its superior speed and reliability.
SetWorkingDir %A_ScriptDir%  ; Ensures a consistent starting directory.

!8::run <shortcut target command> +5

The above script is bound to Alt+8, which is what I use on my mouse. The exclamation mark means alt, the characters afterward are taken literally (8). The double colon acts as a delimiter. There are a full list of modifiers here, you also don't need to use a modifier/key combination - you can just use a single key: https://www.autohotkey.com/docs/Hotkeys.htm