The widespread applicationso fs ubstitutedd iketopyrrolopyrroles (DPPs) call for the development of efficient methods for their modular assembly.H erein,w e presentap-expansion strategy for polyaromatich ydrocarbons (PAHs) by CÀHa ctivationi nasustainable fashion. Thus, twofold CÀH/N-Ha ctivationsw ere accomplishedb y versatile ruthenium(II)carboxylatec atalysis,p roviding stepeconomical access to diversely decorated fluorogenic DPPs that was merged with late-stage palladium-catalyzed CÀHa rylation on the thus-assembled DPP motif.Since their first synthesis, [1] diketopyrrolopyrroles (DPPs) have attracted great attentionf rom researchers from various research arenas, including optoelectronic material sciences [2] and bioimaging. [3] These inconspicuous smallo rganic DPP molecules exhibit versatile propertiesr anging from low solubility, chemicalr esistance, outstanding stabilities and distinct colors, which render them excellent pigments. [4] N-Alkylationl eads to DPPs with improved solubilities,t he properties of which can be fine-tuned by the incorporationo fd ifferent aromatic motifs. [3] Due to their strong electron-withdrawing ability and opticalp roperties, DPPs are widely used as small molecules and conjugated semiconducting polymers in organic solarc ells (OSCs), [2a-e, g, 5] organic field-effect transistors (OFET), [2f, 6] organic photovoltaic cells (OPVs), [7] as well as fluorescentp robes, [3, 8] photocatalysts, [9] photosensitizers [10] or photothermal therapy agents, [11] promisinga nnihilatorm olecules, [12] self-assembled dyes, [13] and bioconjugated hybrids. [14] DPP derivatives with ah ighly decorated periphery as wella s DPP-based polymers are usually obtainedt hrough convention-