Starting with the first-order formulation of the massless superparticle model on the AdS 5 × S 5 superbackground and presenting the momentum components tangent to AdS 5 and S 5 subspaces as bilinear combinations of the constrained SU (2)-Majorana spinors allows to bring the superparticle's Lagrangian to the form quadratic in supertwistors. The SU (2, 2|4) supertwistors are assembled into a pair of SU (2) doublets, one of which has even SU (2, 2) and odd SU (4) components, while the other has odd SU (2, 2) and even SU (4) components. They are subject to the first-class constraints that generate the psu(2|2) ⊕ u(1) gauge algebra. This justifies previously proposed group-theoretic definition of the AdS 5 × S 5 supertwistors and allows to derive the incidence relations with the (10|32) supercoordinates of the AdS 5 × S 5 superspace. Whenever superparticle moves within the AdS 5 subspace of the AdS 5 × S 5 space-time, twistor formulation of its Lagrangian involves just one SU (2) doublet of SU (2, 2|4) supertwistors with even SU (2, 2) and odd SU (4) components. If in addition particle's 5-momentum is null, four first-class constraints which are the su(2) ⊕ u(1) generators single out upon quantization the states of D = 5 N = 8 gauged supergravity multiplet in the superambitwistor formulation.