Electrochemical synthesis is an attractive option for the synthesis of materials because electrocrystallization is faster (microseconds), easier (fewer variables influence structure) and more cost-effective (only requiring an ion source and electrolyte) than traditional chemical methods. Pt and PtAg materials were synthesised using electrochemical techniques, including staircase cyclic voltammetry (CV). Differential pulse amperometry (DPA), square wave voltammetiy (SWV) and second harmonic AC voltammetry (2nd HACV) were employed as pulse potential techniques. Characterisation was conducted using X-ray diffraction, field emission scanning electron microscopy, X-ray fluorescence, cyclic voltammetry in acidic and basic media and by assessing the behaviour of the synthesised materials in oxygen reduction reaction (ORR). For the cyclic voltammetry and DPA techniques, a decrease in the interfacial electrode/solution concentration resulted in the formation of semi-spherical nanoparticles with dendritic nanosheet growth. Semi-spherical Pt nanoparticles with small crystal sizes were obtained using SWV and 2nd HACV due to the enhancement of the Pt seed growth by the low-time pulse potential period. Silver incorporation allowed the formation of well-defined cubic-shaped and flower-like PtAg nanoparticles without the need for surfactants and/or reductants. Silver acted both as a silver ion source and an additive, due to its passivation of the particle surfaces. (C) 2013 Elsevier Ltd. All rights reserved.