An accurate determination of the valence band discontinuity of the lattice matched GaAs/InGaP heterostructure is performed by admittance spectroscopy measurements in p
+/MQW/n
+ structures grown by metal-organic vapour phase epitaxy (MOVPE) using tertiarybutylarsine and tertiarybutylphosphine as alternative precursors for the V group elements. Through the analysis of the temperature dependence of the resonance frequency
at which the isothermal curves of the conductance over frequency
G(
ω)/
ω have the maximum, the energy separation of 336 ± 5 meV between the lowest heavy hole quantum level in the GaAs wells and the InGaP valence band top is obtained. A valence band discontinuity of Δ
EV = 346 ± 5 meV is then derived by accounting for the calculated confinement energy of heavy holes (
). Experimental values of Δ
EV previously reported in the literature spread over the wide range of 300–400 meV.