Temperature-dependent magnetization and magnetoresistance of the Na doped La1−xCax −yNayMnO3 type samples with x = 0.3 and 0 ≤ y ≤ 0.15, showing a rhombohedrally distorted perovskite structure with space group Rbar 3c, have been studied under a pulsed magnetic field. With the increase in temperature from the low temperature ferromagnetic phase, the samples exhibit a sharp metal to insulator transition around Tp accompanied by a ferromagnetic (metallic) to paramagnetic (semiconducting) phase transition with a well defined Curie temperature TC (almost equal to Tp). Interestingly, small Na doping largely increases the conductivity and Tp, which is associated with a decrease of the (e–ph) interaction constant (γ). Doping of monovalent Na in the Ca site of La1−xCax−yNayMnO3 drives the system from a high resistivity regime with lower Tp to a lower resistivity regime with higher Tp values. Low temperature resistivity data fit well the relation ρ = ρ0 + ρ2 T2, signifying the importance of the electron–magnon scattering process (the ρ2 T2 term). On the other hand, the high temperature (T > Tp up to 320 K) conductivity data satisfy the variable range hopping (VRH) model. For T > 320 the small polaron hopping model is more appropriate than the VRH model. Even with a very small change of y, the density of states at the Fermi level N(EF) changes considerably. The resistivity of these materials measured under pulsed and continuous DC magnetic fields behaves in an identical fashion. The relaxation time (decay time of the magnetic pulse within the sample) varies with field strength, which indicates that, with a change of magnetic field, the ordering of spin in the ferromagnetic regime changes.