Recent advances in wireless technology, sensors and portable devices offer interesting opportunities to enable ubiquitous assistance to individuals in need of prompt help. Providing healthcare services to mobile users, such as, patients, elders, or potential drug abusers, is a rather challenging task. Novel middleware-level supports are required to integrate sensor infrastructures capable of detecting changes in the monitored subjects' health conditions and of alerting medical personnel, and the victim's relatives and friends in case of emergency situations. Along this line, the paper envisions a context-aware middleware-level solution dubbed Pervasive Environment for Affective Healthcare (PEACH). PEACH integrates together various sensors in a Wireless Body Area Network (WBAN) to detect alterations of monitored subjects' affective and physical conditions, aggregate the sensed information, and also detect potentially dangerous situations for the monitored subject. Finally, PEACH aims at providing outdoor assistance to the victim/patient by quickly promoting the formation of ad hoc rescue groups comprising nearby volunteers. Through encouraging results obtained from both simulations and a practical drug-rehabilitation application testbed, the effectiveness of the envisioned PEACH framework is verified.