I had a strange coworker in my previous workplace that I was mentally ready to square off during work..
I had a strange coworker in my previous workplace that I was on my toes for anything during work.
ご質問ありがとうございます。
この場合、「square off」と覚えたいなら、下記の英文通りになります。
I had a strange coworker in my previous workplace that I was mentally ready to square off during work.
この文脈で「square off」という表現の代わりに「to be on my toes」でも言えると思います。これは「何かに対して、注意する」という意味です。
ご参考になれば幸いです。