A new family of crystalline microporous silicometallophosphates designated MAPSO-64 and modified forms thereof have been synthesized. These silicometallophosphates are represented by the empirical formula R+rMm2+EPxSiyOz where R is an organoammonium cation such as ETMA+ or DEDMA+, M is an alkaline earth or transition metal cation of valence 2+, and E is a trivalent framework element such as aluminum or gallium. The MAPSO-64 compositions are characterized by a BPH framework topology and have catalytic properties for carrying out various hydrocarbon conversion processes, and separation properties for separating at least one component.