Organometallics are widely used in catalysis and synthesis. Their analysis relies heavily on mass spectrometric methods, among which traveling-wave ion mobility spectrometry (TWIMS) has gained increasing importance. Collision cross sections (CCS) obtainable by TWIMS significantly aid the structural characterization of ions in the gas phase, but for organometallics, their accuracy has been limited by the lack of appropriate calibrants. Here, we propose tetraorganylborates and their alkali-metal bound oligomers [M_n–1(BR₄)_n]⁻ (M = Li, Na, K, Rb, Cs; R = aryl, Et; n = 1–6) as calibrants for electrospray ionization (ESI) TWIMS. These species chemically resemble typical organometallics and readily form upon negative-ion mode ESI of solutions of alkali-metal tetraorganylborates. By combining different tetraorganylborate salts, we have generated a large number of anions in a modular manner and determined their CCS values by drift-tube ion mobility spectrometry (DTIMS) (^DTCCS_He = 81–585, ^DTCCS_N2 = 130–704 Ų). In proof-of-concept experiments, we then applied these ^DTCCS values to the calibration of a TWIMS instrument and analyzed phenylcuprate and argentate anions, [Li_n–1MnPh_2n]⁻ and [M_nPh_n+1]⁻ (M = Cu, Ag), as prototypical reactive organometallics. The ^TWCCS_N2 values derived from TWIMS measurements are in excellent agreement with those determined by DTIMS (<2% relative difference), demonstrating the effectiveness of the proposed calibration scheme. Moreover, we used theoretical methods to predict the structures and CCS values of the anions considered. These predictions are in good agreement with the experimental results and give further insight into the trends governing the assembly of tetraorganylborate, cuprate, and argentate oligomers.