Hi @Jack BaxterThanks for reaching out to Microsoft Q&A.
The Conditional Access feature is applied as an authorization after the first authentication step (user + password), which means that it can be used to grant or block access to an application based on the type (strength) of the authentication method, butyou can't configure the passwordless sign in using CA policy only.
The doc below has more information about passwordless authentication:
https://learn.microsoft.com/en-us/entra/identity/authentication/concept-authentication-passwordless
Another important thing is that the application must support a passwordless method. The link below contains a table with more information about the methods available and their differences
Thanks,
Fabio