In this work, effect of doping of a fixed-valence non-transition metal ion Al3+ on B-site of La2NiO4+delta (LNO) system is investigated by a blocking cell experiment. The mass and charge transport properties of La2Ni0.95Al0.05O4.025+delta (LNAO) in isothermal conditions are investigated and ionic charge of transport (alpha(i)*), which is a measure of cross-effect between ionic and electronic flows and corresponds to the number of electrons dragged by a cation in the absence of the direct cause of electron flow, and partial electronic conductivity under a blocking condition (sigma(e)') is measured and values of Onsager transport coefficients are extracted by constructing an Onsager matrix. alpha(i)* shows a minimum during its variation with oxygen partial pressure (pO(2)) which might be related to the unusual defect structure of LNO systems. Oxygen chemical diffusivities ((D) over tilde (chem)) as a function of pO(2) at different temperatures are extracted from Onsager coefficients to calculate defect diffusivity of interstitial oxygen (D-i) and oxygen self-diffusivity(D-O). D-i values for LNAO are nearly 2 orders of magnitude lower than those for LNO, which might be due to the reduction in free-volume of perovskite layer on Al3+ doping. Partial ionic conductivity (sigma(i)) and oxygen permeation flux (J(O2)) are calculated from Onsager coefficients, and values are compared with LNO. (C) 2016 The Electrochemical Society. All rights reserved.