In this paper, the effects of Dufour and thermal diffusion and on unsteady MHD (magnetohydrodynamic) free convection and mass transfer flow through an infinite vertical permeable sheet have been investigated numerically. The non-dimensional governing equations are solved numerically by using the superposition method with the help of “Tec plot” software. The numerical solution regarding the non-dimensional velocity, temperature, and concentration variables against the non-dimensional coordinate variable has been carried out for various values of pertinent numbers and parameters like the suction parameter $$\left( {v_{0} } \right)$$
v
0
, Prandtl number $$\left( {P_{r} } \right)$$
P
r
, magnetic parameter $$\left( M \right)$$
M
, Dufour number $$\left( {D_{f} } \right)$$
D
f
, Soret number $$\left( {S_{0} } \right)$$
S
0
, Schmidt number $$\left( {S_{c} } \right)$$
S
c
, and for constant values of modified local Grashof number $$\left( {G_{{\text{m}}} } \right)$$
G
m
and local Grashof number $$\left( {G_{r} } \right)$$
G
r
.The velocity field decreases for increasing the suction parameter which is focusing on the common fact that the usual suction parameter stabilizing the effect on the boundary layer growth. The thermal boundary layer thickness becomes thinner for rising values of the Dufour and Soret numbers. The skin friction enhances for uplifting values of Soret number and Dufour number but reduces for moving suction parameter, Magnetic force number, Prandtl number, and Schmidt number. The heat transfer rate increases for increasing the suction parameter, Dufour number, Prandtl number, and Soret number. The mass transfer rate increases for enhancing the values of suction parameter, Magnetic force number, Soret number, and Prandtl number but decreases for Dufour number and Schmidt number.