As I see it, your fundamental issue here is that whatever application layer defence measures you put in place to mitigate this attack can be worked around by the attacker, assuming this really is a malicious attack made by a competent adversary.
In my view, you should definitely be using HTTPS, which in principle would allow the user to confirm for sure whether they're talking to the right server, but this relies on the user knowing to check for this. Some browsers these days display extra information in the URL bar about which legal entity owns the SSL certificate, which would help, as it's unlikely an attacker would be able to persuade a legitimate certificate authority to issue a certificate in your name.
Some of the other comments here said that HTTPS can be intercepted by intermediate proxy servers, which is not actually true. With HTTPS, the client issues a CONNECT request to the proxy server, which tunnels all future traffic direct to the origin server, without being able to read any of it. If we assume that this proxy server is entirely bespoke and malicious, then it can terminate the SSL session and intercept the traffic, but it can only do that with its own SSL certificate, not with yours. This certificate will either be self signed (in which case clients will get lots of warning messages) or a genuine certificate issued by a certificate authority, in which case it'll have the wrong legal entity name, and you should be able to go back to the certificate authority, have the cert revoked and potentially ask the police to take action against the owner of the certificate, if you have reasonable suspicion that they are phishing.
The other thing I can think of which would mitigate this threat to some extent would be to implement one-time password functionality, either using a hardware/software token or using (my personal favorite) an SMS sent to the user's phone when they log in. This wouldn't prevent the attacker getting access to the session once, but should prevent them being able to log in in future. You could further protect the users by requiring another one time password before allowing them to see/edit particularly sensitive details.