I’ve been using PTT for a while, and I have it bound to my mouse side button.
I decided to switch to open mic so it’s a little easier to chat in high pressure moments. I rebound my mouse side button to the toggle mute. While in menu, it worked fine, but in game it wouldn’t work and I had to use M. Not sure why it was doing that but it was only during a game, it simply would not work. I don’t know if it matters, but I’m using a Logitech g502
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Are you sure that you changed the setting for every character? I had a similar issue and it turned out that since I had custom settings for most characters just changing the voice chat button in the general settings didn’t affect them…I had to go through each character’s settings separately.
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I just got this too, here is the technicalities:
BLIZZARD: Your key definition gets loaded and is used properly while you are in char select, or watching a replay as to how you were killed.
However it gets overwritted while in game.
This effectively means you can only use “M” to mute or unmute open mic, you can’t use any other key for that while in a match. the key you set it to will work everywhere else.
This is so annoying, and should be a partially easy fix. Please check into this? this has been going on for a long long time
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Found the answer here: Overwatch Forums
Set your push to mute button in the blizzard launcher settings to the same as in overwatch. Fhat fixed it for me.
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Didn’t want to bring up a super old post but this bug is still there. come on blizz…
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Not sure if this would work. but I forgot to set my setting to open mic and then I changed my keybinding on to the toggle mute. and it fixed my issue
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Hello! I know this is “necroing” but I have the same issue as you described, as for today January the 22nd of 2021. It’s a weird issue that only (very unearthly) happens sometimes, though.
I use a deathadder elite and I also have the toggle open mic button assigned to my mouse. I think it’s a game bug too as we use different mice.
If you have discovered any fix I’ll be pleased to read your ideas. Have a good day 
Thank you, this fixed it for me