Decomposing litter is regarded as the most important source of allelochemicals released into soil. In this study, a greenhouse experiment was designed to assess the net effect of differently aged leaf litter from exotic (Ailanthus altissima, Robinia pseudoacacia and Ulmus pumila) and native riverine trees (Populus alba, Populus nigra and Ulmus minor) on the germination and growth of three herb species (Trifolium repens, Dactylis glomerata and Chenopodium album). We also characterized the chemical composition of litter samples at different litter ages (0, 1, 2 and 3 months) based on phenolic compounds, fibers and ergosterol (as a measure of fungal biomass) contents. Overall, litter from both native and exotic species had a negative effect on shoot and root growth of target species, indicating that phytotoxic effects of litter predominate over positive effects. The inhibition effect of the exotic species was similar or even lower than that of the natives, which does not support the Novel Weapons Hypothesis. Among exotic trees, U. pumila showed the highest inhibition effect on the growth of the target species. T. repens was the most sensitive target species. The importance of litter age varied with both target and donor species. In general, D. glomerata was more inhibited by fresh litter, C. album by half-decomposed litter of U. pumila and R. pseudoacacia and by fresh litter of A. altissima and T. repens was more inhibited by fresh litter of A. altissima and P. alba and by highly decomposed litter of U. minor. The concentration of total phenolics and flavonoids decreased while acid detergent fiber, lignin and ergosterol increased with increasing litter age. Hydroxybenzoic and protocatechuic acids and the flavonoid quercetin were detected in all litter species and at most of the litter ages, while gallic, chlorogenic, vanillic, coumaric and rosmarinic acids were species-specific and they were only detected in fresh litter. Ergosterol concentration appeared as the strongest constrictor of inhibitory effects of litter on understory species. The results of this study contribute to the understanding of the net effect of fresh and decomposed litter from exotic and native trees on the growth of understory species.