•Use of a 10dm3 solar plant with a FM01-LC cell and a CPC photoreactor.•Predominant H2O2 production at the graphite-felt cathode and photolysis at the CPC.•Close agreement was obtained between theoretical and experimental data.•Four heterocyclic, one aromatic, one tertiary amine and five carboxylic acids detected.•Release of nitrate ions and, to a lesser extent, ammonium ion. A solar photoelectro-Fenton (SPEF) plant containing a filter-press FM01-LC flow reactor in series with a compound parabolic collector (CPC) as photoreactor, operating in batch recirculation mode, was simulated using a parametric model. The degradation of 10dm3 of solutions of the heterocyclic antibiotic erythromycin (ERY) in 0.050moldm−3 Na2SO4 at pH 3.0 was used for validation. The filter-press reactor contained a platinized titanium plate anode and a graphite-felt cathode that produced H2O2 from the reduction of dissolved oxygen (0.24mmoldm−3). Trials were performed under potentiostatic and galvanostatic conditions with predominance of H2O2 production, minimizing H2 evolution reaction. The effect of initial catalyst (Fe2+) concentration, current density (j), initial antibiotic concentration as dissolved organic carbon (DOC) and volumetric flow rate on the ERY mineralization was studied. Good agreement between simulations and experimental DOC decays was obtained. Mineralization current efficiencies and specific energy consumptions were also determined. The best performance under galvanostatic conditions was found for 0.225mmoldm−3 ERY (100mgdm−3 DOC), 0.50mmoldm−3 Fe2+, volumetric flow rate of 3.0dm3min−1 and jcath=-0.16mAcm−2, reaching 69% mineralization with current efficiency of 75% and specific energy consumption of 0.059kWh (g DOC)−1. Six organic by-products were identified by gas chromatography-mass spectrometry, whereas final short-chain carboxylic acids like formic and oxalic acid were detected by ion-exclusion high-performance liquid chromatography. The initial N atom of ERY was predominantly converted into NO3− ion, although NH4+ ion was formed as well.