β-Substituted ferrocenyl porphyrins were designed and synthesized by the Pd-catalyzed Sonogashira cross-coupling reaction. The UV-vis absorption, emission, and cyclic voltammetric results indicate strong electronic communication between ferrocene and porphyrin. The porphyrin 4a is non-emissive in nature, while 4b and 4c show reduced fluorescence quantum yield. The single crystal X-ray structure of 4b is reported, which shows extensive C–H–π interactions.