Four series of new push–push–pull chromophores based on two types of heterocyclic cores, namely imidazo[5,1,2‐cd]indolizines and naphtho[1′,2′:4,5]imidazo[1,2‐a]pyridines, and two types of linear π spacers, namely diphenylacetylene and biphenyl, were prepared. The two isomeric heterocyclic compounds were prepared by palladium‐catalyzed double C–H functionalization reactions. Further palladium‐catalyzed C–C coupling reactions allow the construction of diphenylacetylene and biphenyl spacers on the chromophores. Different electron‐donors including NMe2, NPh2, and OMe and CN acceptors were incorporated into the chromophores. The corresponding donor‐ and acceptor‐free compounds were also prepared for comparative studies. In the case of chromophores with strong NMe2 or NPh2 donors, a strong intramolecular charge‐transfer (ICT) process occurs leading to fluorescence emission quenching in polar solvents. The use of a slightly weaker OMe donor together with the naphtho[1′,2′:4,5]imidazo[1,2‐a]pyridine core allows to obtain an intense blue fluorescence with high quantum yield of up to 0.825. DFT and TD‐DFT calculations offer satisfactory explanations to the observed photophysical data.