A new set of free‐base and zinc(II)‐metallated, β‐pyrrole‐functionalized unsymmetrical push–pull porphyrins were designed and synthesized via β‐mono‐ and dibrominated tetraphenylporphyrins using Sonogashira cross‐coupling reactions. The ability of donors and acceptors on the push–pull porphyrins to produce high‐potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β′‐pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady‐state and time‐resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push–pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π‐system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one‐electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push–pull porphyrins to produce charge‐separated states upon photoexcitation was confirmed and the measured rates were in the range of 10⁹ s⁻¹. The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push–pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high‐potential charge‐separated states are warranted.