Addressed herein is the in situ synthesis of a PAMAM dendrimer-encapsulated palladium(0) NPs (Pd(0)/Dnd) during the methanolysis of ammonia borane (AB) and the catalytic performance of the yielded Pd(0)/Dnd nanocatalysts in hydrogen production from the methanolysis of AB under ambient conditions. A two-step procedure that includes the impregnation of Pd(II) ions via their coordination to -NH2 groups of the dendrimer and then reduction of Pd(II) ions into the dendrimer-encapsulated Pd(0) NPs by AB during the methanolysis reaction was followed for the synthesis of Pd(0)/Dnd nanocatalysts. However, apart from the existing reports on the synthesis of dendrimer-encapsulated metal NPs, the present study includes for the first time the examination of effect of generation size (G4-G6), core type (ethylene diamine (E) or Jeffamine (P)) and terminal groups (-NH2, -COOH and -OH) of a PAMAM dendrimer on the stability, particle size, morphology and catalytic activity of metal NPs. After finding the optimum Pd(0)/Dnd catalysts considering all these effects, a detailed kinetic study comprising the effect of catalyst and AB concentrations as well as temperature was conducted by monitoring the hydrogen production from the methanolysis of AB. The best catalytic activity in the methanolysis of AB was obtained by using a PAMAM dendrimer with generation G6, amine terminal groups and Jeffamine core (P6.NH2) encapsulated Pd(0) NPs, providing the highest initial turnover frequency (TOF) of 55.8 mol H-2.mol pd(-1).min(-1) and apparent activation energy (Ea(app)) of 48 +/- 3 kJ.mol(-1) at room temperature. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.