We show here a strategy to predict the crystal structure, formulate, and prepare new noncentrosymmetric (NCS) bismuth-phosphate based compounds. It is based on the cooperative-arrangement of polar building units (BUs) which can be created at particular stoichiometric conditions. The arrangement of such BUs into NCS compounds arise from the shortest-periodicity of repartition of the cationic charges in NCS structures than in the plausible, but never observed centrosymetric polytypes. This work validates the possibilities for the prediction of an extended series of novel compounds, tuning the size of BUs within a variety of controlled edifices. Despite their closed chemical composition, all the predicted terms appeared strikingly stable at precise stoichiometries.