Be wary of people who praise you to your face.

Literal

Face-to-face-at praise person [topic-は] beware-[command-なさい].

面と向かって ('face to face') is a fixed adverbial phrase, literally 'facing-face.' The relative clause 面と向かって誉める people serves as the topic. 用心する ('to be cautious, to watch out') is a slightly more formal alternative to 気をつける.