PhySyQX is a multimodal database, developed for neuro-physiological identification of the human factors which influence user perceived quality-of-experience (QoE) and also to probe into the users’ internal quality formation processes. It is hoped that the database will help improve the pre-existing models for quality estimation. The database utilizes 62-channel electroencephalography (EEG) and 60-channel functional near infrared spectroscopy (fNIRS), to record users’ brain activity while experiencing synthesised speech produced from various commercially available TTS systems along with four different natural voices. The data was recorded for 21 (8 females) participants. Moreover, the database consists of participants’ ratings for 12 different subjective dimensions (including affective dimensions of valence, arousal and dominance) which were used to characterize speech QoE. Along with this, the speech files used as stimuli have also been made available (except for 2 natural voices). This database has been made publicly available online to encourage other researchers to utilize the neuro-physiological insights while developing new quality estimation algorithms or characterizing users affective states.