In this work, a systematic investigation of the alloying behavior on the M sub-lattice of M 2 AlC, where M is Ti,V,Zr and Hf with elements in the first transition metal row as well as Ca and Sc is carried out via a combination of alloy theoretic approaches and Density Functional Theory for 41 alloy systems. The cluster expansion formalism is used to explore the configurational space in ternary MAX phases. On the basis of their solid-solution behavior, the alloys are classified into three regimes: phase separation, weak ordering and strong ordering. Observed trends are investigated in terms of indicators at the electronic and structural levels. For the systems showing ordering, the ordered structures are identified and their structural and electronic properties are investigated. The likelihood of some of the systems to exist as solid solutions at finite temperature is discussed.