Different cyclic (alkyl)(amino)carbenes (CAACs) were reacted with yellow arsenic. Several products [(CAAC-n)(2)(mu,eta(1:1)-As-2)] (n=1 (1), 4 (2)), [(CAAC-2)(3)(mu(3),eta(1:1:1)-As-4)] (3) and [(CAAC-3)(4)(mu(4),eta(1:1:1:1)- As-8)] (6) were isolated due to the differing steric properties of CAAC-1-4. The products contain As-2, As-4 or As-8 units and represent the first examples of CAACs-substituted products of yellow arsenic. The reactivity of As-4 was compared with the reactivities of P-4 and the interpnictogen compound AsP3, which led to a series of phosphorus-containing derivatives such as ([(CAAC-3)(3)(mu(3),eta(1:1:1)-P-4)] (4) and [(CAAC-3)(4)(mu(4),eta(1:1:1:1)-P-8)] (7)) and [(CAAC-3)(3)(mu(3),eta(1:1:1)-AsP3)] (5). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.