Mixed-dimensional (0D/2D) van der Waals heterojunctions were constructed by physical adsorption of anthracene (Anth) onto few-layer MoS2 nanosheets. The physical modification of few-layer MoS2 nanosheets using anthryl dendron 1, i.e., a poly(amidoamine) dendrimer having an anthracene core, via a simple yet efficient exfoliation approach afforded MoS2/1 hybrids, which are stable for at least one month. The emission quenching typical for anthracene is also observed in the MoS2/anthracene mixed-dimensional heterojunctions. Transient absorption measurements on MoS2/1 hybrids proved that photoinduced electron transfer occurs at the MoS2/anthracene interface. The lifetime of the singlet excited state (tau(S1)((1)Anth*)) for MoS2/1 was evaluated to be 4.1 ns, which is shorter than that of anthryl dendron 1 (13 ns). Interestingly, a remarkably long lifetime was observed for the anthracene cation radical (6.1 mu s). Relatively long lifetimes of charge-separate states of MoS2/1 hybrids would be beneficial design features for efficient photovoltaics, photocatalysts, and related optoelectronic applications.