Volcanic eruptions can alter the quality of incoming solar irradiance reaching the Earth's surface thereby influencing the interactions between vegetation and the Earth system. Isoprene (C<sub>5</sub>H<sub>8</sub>) is a biogenic volatile organic compound emitted from leaves at a rate strongly dependent on the received flux of photosynthetically radiation radiation (PAR). We investigated the potential for volcanic eruptions to change the isoprene flux from terrestrial vegetation using canopy-scale isoprene emission simulations that vary either the relative or absolute amount of diffuse (<i>I</i><sub>diff</sub>) and direct (<i>I</i><sub>dir</sub>) PAR. According to our simulations, if the total amount of PAR remains constant while the proportion of <i>I</i><sub>diff</sub> increases, canopy-scale isoprene emissions increase. This effect increases as leaf area index increases. Simulating a~decrease in the total amount of PAR, and a corresponding increase in <i>I</i><sub>diff</sub> fraction, as measured during the 1992 Pinatubo eruption, decreases daily total canopy-scale isoprene emissions from terrestrial vegetation by 17–19% (for leaf area indices of 6 and 2, respectively). These effects have not previously been realized or quantified. Better capturing the effects of volcanic eruptions (and other major perturbations to the atmospheric aerosol content) on isoprene emissions from the terrestrial biosphere, and hence on the chemistry of the atmosphere, therefore requires inclusion of the effects of aerosols they produce on climate and total PAR and the <i>I</i><sub>diff</sub>/<i>I</i><sub>dir</sub> ratio.