Four new low-dimensional phenylarsonates, A(HO₃AsC₆H₅)(H₂O₃AsC₆H₅) (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 compounds1 and2 with primaryn-alkyl amines have been demonstrated.