Aluminum was incorporated into the layered silicate RUB-39, which is transformed by calcination into RUB-41. This new zeolite with RRO topology contains 8- and 10-ring pores, and the acid sites in the aluminated material catalyze the synthesis of methylamines, in particular mono- and dimethylamine, by amination of methanol. Owing to the shape-selective catalytic properties of (H)Al-RUB-41, low selectivity to the thermodynamically favored trimethylamine product is obtained in comparison with results on RUB-39 or non-shape-selective materials. Both activity and selectivity are highest for RUB-41 catalysts with a high Si to Al ratio. Silylation reduces the number of unselective sites and results in a further suppression of trimethylamine formation. The introduction of acidity in the intact RUB-41 structure is supported by Al-MAS NMR and NH(3)-TPD data. Additional characterization by XRD and SEM is provided. (C) 2010 Elsevier Inc. All rights reserved.