Ab initio (MP2/6-311 + G*) and density functional theory (B3LYP/6-31 I + G*) calculations have been performed to determine the bonding nature of N, P, and As (pnicogens) with B or C in ylides and their boron analogues. The compounds studied refer to the formulas R3XCR'(2) and R3XBR' (X = N, P, As; R = H, F; R' = H, SiH3). The computed electron density has been analyzed by means of the atoms in molecules (AIM) theory and the electron localization function (ELF) method. In addition, the rotational barriers were calculated for X-C and X-B bonds at the CASMP2/6-311 + G* level to elucidate the multiple bonding character for these bonds. The geometric and electronic results indicated that the N ylides differ remarkably from the remaining pnicogen (P, As) ylides, with the former yielding clear single bonds while the latter showed stronger multiple bonds. Moreover, the fluorine substituents strengthened the X-C and X-B bonds, reducing the bond distance, increasing the electron density, and augmenting the planarity at the C and B atoms. However, the SiH3 groups affected only the planarity at the C atoms for the organic ylides. This indicates how the electronegativity of the different substituents influence the central X-C and X-B bonds: if the substituent pulls charge from the bond in the direction toward the pnicogen, the bond is reinforced and it is more likely to present double-bond characteristics. This is not accomplished by substituents pushing charge in the aforementioned direction. Differences between the organic ylides and their boron derivatives have been found. Boron analogues presented remarkable asymmetric X-B bonds, with a rotation barrier of ca. 30 kcal/mol, caused by a strong repulsion between the lone pairs of the XH3 unit and that of boron.