75 As and 45 Sc NMR measurements unravel the electronic state for Fe-based superconductors with perovskite-type blocking layers Ca4(Mg,Ti)3Fe2As2O8−y (T onset c = 47 K) and Ca5(Sc,Ti)4Fe2As2O11−y (T onset c = 41 K). In Ca5(Sc,Ti)4Fe2As2O11−y, the nuclear spin relaxation rate 1/T1 shows pseudogap behavior below ∼ 80 K, suggesting that the electronic state is similar to that of LaFeAs(O,F) system with moderate electron doping. The presence of the pseudogap behavior gives an interpretation that the hole-like band (so-called γ pocket) is located just below the Fermi level from the analogy to LaFeAs(O,F) system and the disappearance of the γ pocket yields the suppression of the low-energy spin fluctuations. On the other hand, in Ca4(Mg,Ti)3Fe2As2O8−y satisfying the structural optimal condition for higher Tc among the perovskite systems, the extrinsic contribution, which presumably originates in the Ti moment, is observed in 1/T1T ; however, the moderate temperature dependence of 1/T1T appears by its suppression under high magnetic field. In both systems, the high Tc of ∼ 40 K is realized in the absence of the strong development of the low-energy spin fluctuations. The present results reveal that the structural optimization does not induce the strong development of the low-energy spin fluctuations. If we consider that superconductivity is mediated by spin fluctuations, the structural optimization is conjectured to provide a benefit to the development of the high-energy spin fluctuations irrespective to the low-energy part.