Second-order nonlinear optics is the base for a large variety of devices aimed at the active manipulation of light. However, physical principles restrict its occurrence to non-centrosymmetric, anisotropic matter. This significantly limits the number of base materials exhibiting nonlinear optics. Here, we show that embedding chromophores in an array of conical channels 13 nm across in monolithic silica results in mesoscopic anisotropic matter and thus in a hybrid material showing second-harmonic generation. This nonlinear optics is compared to the one achieved in corona-poled polymer films containing the identical chromophores. It originates in the confinement-induced orientational order of the elongated guest molecules in the nanochannels. This leads to a non-centrosymmetric dipolar order and hence to a nonlinear light–matter interaction on the sub-wavelength, single-pore scale. Our study demonstrates that the advent of large-scale, self-organized nanoporosity in monolithic solids along with the confinement-controllable orientational order of chromophores at the single-pore scale provides a reliable and accessible tool to design materials with a nonlinear meta-optics.