Herein, we report results from our studies on the ultrafast nonlinear optical (NLO) properties and excited-state dynamics in three different porphyrin molecules designed in D-π-D fashion (phenothiazine-porphyrin-phenothiazine) and with two different central metal ions [Zn(II) and Cu(II)]. We have performed extensive target analysis of the femtosecond transient absorption data obtained conveying the true exited state/species spectra of each process with respective lifetimes along with microscopic rate constants of each excited state. The obtained life time values were in the range of 250–500 fs, 20–142 ps, 1.5–6.2 ns and 0.1–1.23 μs and have been associated from relaxation with the Sn, Hot S1 (to S1), S1, and T1 states. Furthermore, the third-order nonlinear (NLO) coefficients [two-photon absorption (TPA) and nonlinear refractive index (n2)] of CPPHT and ZPPHT exhibited superior values compared to HPPHT recorded with ~50 fs, 1 kHz repetition rate pulses at a wavelength of 800 nm. The magnitude of the TPA coefficients of these molecules was compared with some of the recently reported porphyrin moieties and were found to be superior. The time-resolved degenerate four-wave mixing (DFWM) measurements confirmed a large magnitude and an ultrafast response of the χ(3) in these molecules suggesting potential photonic and all-optical switching applications. © 2020 Elsevier B.V.