The conditions for the growth of (Perylene)(2) [Pd(mnt)(2)] crystals either by chemical oxidation and electrochemical routes are described. The electrocrystallisation is limited by close proximity of the oxidation potentials of the perylene donor and [Pd(mnt)(2)](-) anion, and depending on the experimental conditions different morphologies can be obtained. (Per)(2) [Pd(mnt)(2)] crystals obtained by elecrocrystallisation were found to be mainly of the beta-polymorph with properties comparable to the Cu, Ni and Pt analogues previously described at variance with those obtained by chemical oxidation which are mainly of the alpha-polymorph. (c) 2011 Elsevier B.V. All rights reserved.