Wearable systems for monitoring biological signals have opened the door to personalized healthcare and have advanced a great deal over the past decade with the development of flexible electronics, efficient energy storage, wireless data transmission, and information processing technologies. As there are cumulative understanding of mechanisms underlying the mental processes and increasing desire for lifetime mental wellbeing, various wearable sensors have been devised to monitor the mental status from physiological activities, physical movements, and biochemical profiles in body fluids. This review summarizes the recent progress in wearable healthcare monitoring systems that can be utilized in mental healthcare, especially focusing on the biochemical sensors (i.e., biomarkers associated with mental status, sensing modalities, and device materials) and discussing their promises and challenges.