This study investigates the effectiveness of non-activated peroxymonosulfate (PMS) as oxidative agent for water purification in the presence and absence of natural solar radiation. The inactivation of three pathogens (Escherichia coli, Enterococcus faecalis and Pseudomonas aeruginosa) and degradation of three Contaminants of Emerging Concern (CECs) (Trimethoprim-TMP, Sulfamethoxazole-SMX and Diclofenac-DCF) was simultaneously assessed in isotonic water (IW) by testing a wide range of PMS concentrations (from 0.0001 to 0.01 mM). A significant oxidative effect of PMS in darkness was obtained for both bacteria and CEC abatement, but when irradiated with solar light, results demonstrated a great enhancement on all bacterial kinetic rates, reaching >5 Log reduction in 30 min (1.5 kJL(-1) of Q(UV)) with 0.005 mM of oxidant as the best concentration. For CECs, higher degradation performance was obtained with 0.01 mM, 80% removal of DCF, SMX and TMP was achieved in 16 min (1.5 kJL(-1)), 27 min (9.4 kJL(-1)) and 150 min (16.8 kJL(-1)), respectively. Besides, the influence of inorganic species on the global PMS/solar system performance was assessed by testing its effectiveness in distilled water (DW), natural well water (WeW) and diluted well water (d-WeW) at 0.01 mM. Results revealed that (i) high chloride concentration (IW) has an important positive effect, (ii) the presence of a complex inorganic chemical water composition reduced the system efficiency (WeW), and (iii) no differences were obtained from the presence of low or high contents of carbonates/bicarbonates (WeW versus d-WeW), obtaining the following global PMS/solar efficiency performance order: IW > DW > WeW = d-WeW. (C) 2021 The Authors. Published by Elsevier Ltd.