Why does this issue happen?
Here are some causes accounting for it:
1.
Outdated Windows version
2.
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Mach2 or other similar tool breaks the legitimate dark mode
3.
Dark theme glitch
Then, lets move to fix the Windows 10 File Explorer dark theme not working issue.
To do that, like refer to the following tutorial.

Step 1:OpenSettingsand then clickUpdate & Security.
Then your Windows will start checking for the available Windows 10 updates and then download them automatically.
Thus, you should probably switch to the default theme.

Here is how to do that:
Step 1:Open theSettingsapplication and navigate to thePersonalizationsection.
Step 2:ClickThemesfrom the menu on the left.
In the right pane, selectWindowsfrom theChange themepart.
Step 1:OpenTask Manager.
Step 2:In the pop-up window, find theWindows Explorerprocess.
Right-click it to chooseRestart.
Fix 4: Create a New User Account
Step 1:ClickStartand then clickSettings.
Step 2:ChooseFamily & other usersand then clickAdd someone else to this PCunder theOther userssection.
Step 4:Enter a newUser nameandpassword(optionally), then clickNextto finish creating a new user account.
Step 6:Change theAccount typefromStandard UsertoAdministratorand then clickOKto save changes.
Step 7:Log off from the current user account and log on with the new account.