The relative momentum of electron pairs in atoms and small molecules is examined through calculation of the p(1) . p(2) probability distribution. The likelihood of aligned or antialigned momenta between paired electrons is determined from the calculated distributions. Coulomb correlation aligns the momenta of electron pairs, and the amount of alignment varies when considering momenta in specific directions in three-dimensional space. A static electric field is found to have competing effects on momentum alignment parallel and perpendicular to the electric field. However, the net effect of the electric field on alignment is significantly smaller than the effect of Coulomb correlation. Recent experimental advances suggest that such a correlation of electron momenta can now be measured directly using attosecond spectroscopic tools.