Advanced functional hybrids based on carbon materials (CMs) represent one of the main achievements of scientific communities. To achieve the hybridization, pristine CMs have to be chemically modified, or surfactants, which are nonfunctional for the performances of the hybrids, have to be employed as cross-linkage. It is strongly desired to construct pristine CMs-based hybrids using dual-functional coupling reagents, which work not only as a glue for hybridization but also as functional component for an enhanced performance. Here, we report that pristine graphdiyne (GD), a recently synthesized new carbon allotrope, could be facilely hybridized with Ag/AgBr using graphene oxide (GO) as cross-linkage. We demonstrate that compared to Ag/AgBr, Ag/AgBr/GO, and Ag/AgBr/GD, our Ag/AgBr/GO/GD exhibits boosted photocatalytic performances toward the degradation of methyl orange (MO) pollutant under visible-light irradiation. In our Ag/AgBr/GO/GD, GO severs not only as glue for a successful hybridization but also as functional component for the enhanced catalytic performances. Beyond GD, our work likely paves new avenue for the fabrication of advanced functional hybrids based on pristine carbon allotropes, wherein desired functions or properties might be achieved by choosing desired CMs and desired hybridized components.