Honest signalling theory suggests that humans and chimpanzees can extract socially relevant information relating to personality from the faces of their conspecifics. Humans are also able to extract information from chimpanzees’ faces. Here, we examine whether personality characteristics of chimpanzees, including measures of psychopathy, can be discerned based purely on facial morphology in photographs. Twenty-one chimpanzees were given naïve and expert personality ratings on the Ten Item Personality Inventory (TIPI) and the Chimpanzee Triarchic Model of Psychopathy (CHMP-Tri) before and following behavioural observations. Characteristics relating to openness, conscientiousness, extraversion, and disinhibition could be distinguished from the faces of chimpanzees. Individuals higher on disinhibition have lower scores on conscientiousness and emotional stability and higher scores on extraversion, while those higher on meanness have lower conscientiousness and agreeableness. Facial expressions are linked to personality traits present in the TIPI and CHMP-Tri models: the Relaxed Face and the Grooming Face were displayed more by chimpanzees higher on agreeableness, whereas the Compressed Lips Face was observed more in those individuals higher on boldness, and the Full Open Grin was displayed more by chimpanzees higher on extraversion but lower on emotional stability and conscientiousness. Facial expressions were also found to be associated with particular behavioural contexts, namely the Grooming Face in affiliative contexts and the Relaxed and Relaxed Open Mouth Faces in neutral contexts. Dominant chimpanzees display higher levels of boldness and more Compressed Lips Faces, Relaxed Open Mouth Faces, and Grooming Faces than subordinate individuals. These findings support and extend evidence for an honest signalling system and a personality structure shared between humans and chimpanzees. Future research could further explore how personality is conveyed through the face, perhaps through more than just singular aspects of character, and maybe reflecting what chimpanzees themselves are able to do.