The combined characterization of structural and optical properties of organic interfaces adsorbed on inorganic solid substrates down to the molecular scale is crucial from a fundamental point of view, but also if one tackles efficient applied devices. In this work, a set of joint structural and optical analyses of self-assemblies of π-conjugated bis-pyrene derivatives upon adsorption on two alkali halides bulk insulators is reported. The structural analysis is performed by means of noncontact atomic force microscopy in ultrahigh vacuum either at room or at the liquid-nitrogen temperature with molecular resolution. The surface coverage ranges from the submonolayer (ML) regime up to 5 ML. In situ optical spectroscopy is performed by means of differential reflectance (DR) spectroscopy. A thorough fitting methodology of the DR spectra allows us to derive the complete dielectric function of the molecular adlayers treated in an anisotropic formalism, albeit restricted to an uniaxial approximation. Conclusions regarding the process of condensation of the molecules into H aggregates from its early stages up to the solid molecular phase are drawn. This work highlights three main reasons to bridge high-resolution structural and optical characterization of the molecular layers, which all point towards the necessity to constrain the fitting process, namely, (i) characterizing the growth mode of the molecules, (ii) identifying the structural order of the resulting assemblies, and (iii) discriminating their constitutive phases by means of molecular resolution imaging.