Over the last decade, passive brain-computer interface (BCI) algorithms and biosignal acquisition technologies have experienced a significant growth that has allowed the real-time analysis of biosignals, with the aim to quantify relevant insights, such as mental and emotional states, of the users. Several passive BCI-based applications have been tested in laboratory settings, and just a few of them in real or, at least, simulated but highly realistic settings. Nevertheless, works performed in laboratory settings are not able to take into account all those factors (artefacts, non-brain influences, other mental states) that could impair the usability of passive BCIs during real applications, naturally characterized by higher complexity. The present review takes into account the most recent trends in using advanced passive BCI technologies in real settings, especially for real-time mental state evaluations in operational environments, evaluation of team resources, training and expertise assessment, gaming and neuromarketing applications. The objective of the work is to draw a mark on where we are to date and the future challenges, in order to make passive BCIs closer to being integrated into daily life applications.