Four new low-dimensional phenylarsonates, A(HO3AsC 6H5)(H2O3AsC6H 5) (A = Tl(1), Na(2), K(3) and Rb(4)), have been synthesized and characterized by X-ray diffraction, spectroscopic and thermal studies. They crystallize in triclinic unit cells and have approximately planar arrangement of A+ ions, coordinated to oxygen atoms of phenylarsonates, on both sides. Structure of thallium phenylarsonate as determined by single crystal X-ray diffraction, is one-dimensional, whereas those of alkalimetal analogues are two-dimensional. Successful intercalation reactions of compounds 1 and 2 with primary n-alkyl amines have been demonstrated. © Indian Academy of Sciences.