Affective computing (AfC) is a novel computing paradigm that builds on the results of artificial intelligence, biomedical engineering, and psychology to allow computer systems to detect, use, and express emotions. AfCAI2016 (Affective Computing and Context Awareness in Ambient Intelligence) was a two day workshop held in Universidad de Murcia, Spain, on 24-25 November 2016. It was organized by Maria Trinidad Herrero Ezquerro, Grzegorz J. Nalepa, and José Tomás Palma Méndez. The focus of the workshop was on the intersection of computer science and experimental sciences, including affective computing (AfC), ambient intelligence (AmI), context aware systems (CaS), neurobiological approaches for AfC, psychological and philosophical models of emotions and affects, physiological measurements for affect detection, emotive user interfaces, data mining and knowledge discovery methods for AfC and AmL, mobile platforms for contextaware affective systems, mixed (virtual/augmented) reality environments for affect generation and acquisition, and affective games. The objective of the workshop was to bring together scientists interested in research on affective computing, and the above mentioned topics. We assumed goal oriented yet multidisciplinary research approach, including computer science, artificial intelligence, biomedical engineering, and experimental sciences. We considered both fundamental and applied research with participation of companies where possible. The objective of the workshop was also identifying opportunities for cooperation and EU project applications. In the workshop scientists and researchers from Spain, Poland, Germany and South Korea gave their presentations on the topics of Context Awareness for Ambient Intelligence, Affective Characters in Narrative Contents, Games Technology and Design: Serious Games, Virtual Reality, and Emotive Interfaces, as well as BioInspired and Evolutionary Computation, Affective Information Systems, and finally, AfC Experiments in Virtual Reality with Wearable Sensors. The organizers wish to express their gratitude for the support of the workshop to: Universidad de Murcia, Fundacion SeNeCa, Ilustre Colegio de Médicos de la Región de Murcia, Real Academia de Medicina y Cirugía de la Región de Murcia.