The photolytic and photocatalytic transformation of tiapride with the use of TiO2 and H2O2 was investigated. A novel micro-scale method for simultaneous irradiation with simulated full solar spectrum of multiple samples in photostability chamber was proposed. RP-UHPLC-DAD coupled with ESI-Q-TOF mass spectrometer was used for the quantitative and qualitative analysis of the processes. Quantitative method was fully validated, and kinetic parameters of tiapride photodegradation were compared. Structures of twenty-one photoproducts as well as phototransformation pathways were proposed. Based on the elucidated structures, computational toxicity assessment with the use of various software was performed and some of transformation products were found as a potentially highly mutagenic and carcinogenic compounds. The multivariate statistical method (principal component analysis) was used to compare toxicity of phototransformation products as well as toxicity assessment.