This paper describes a systematic study of the effect of various spray pyrolysis parameters, such as temperature, solution concentration and solution flow rate on the morphology, crystallization process, crystal size, specific surface area and electrochemical performance of in situ prepared α-PbO spherically agglomerated nano-structured powders. Different analytical methods such as XRD, SEM, TEM, BET gas sorption specific surface area measurements and electrochemical tests were performed. Crystallites in the range of 20–120nm and easily dispersed powders were reproducibly prepared by optimization of the spray conditions. An increase of the temperature from 600 to 800°C was found to lead to a three times increase in the average crystal size, from 31 to 102nm. An increase of concentration from 0.15 to 0.5M dramatically suppresses the crystal size from 127 to 25nm. The BET surface area of sprayed PbO powders is increased up to 6.6m2 g−1. For such PbO powders applied as anode materials in Li-ion batteries, we have managed to retain a reversible capacity above 60mAhg−1 beyond 50 cycles.