The blocking version of the Web Request API exists in Manifest V3, but it can only be used by extensions that are force-installed using Chrome's enterprise policies: ExtensionSettings, ExtensionInstallForcelist.
Extensions meant to be used by the general public must now use Declarative Net Request for network request modification. Here 'used by the general public' means any extension published to the Chrome Web Store except those deployed to a given domain or to trusted testers.
The migration checklist also mentions:
Are you currently using the blocking version of chrome.webRequest?
This API is replaced by declarativeNetRequest in Manifest V3.
This only applies to user-installed extensions; force installed extensions (extensions distributed using ExtensionInstallForcelist). These extensions — typically used in an enterprise setting — can still use the blocking version of chrome.webRequest.