An asymmetric pair of coupled nonlinear Schrödinger (CNLS) equations has been derived through a multiscale perturbation method applied to a plasma fluid model, in which two wavepackets of distinct (carrier) wavenumbers ($$k_1$$
k
1
and $$k_2$$
k
2
) and amplitudes ($$\Psi _1$$
Ψ
1
and $$\Psi _2$$
Ψ
2
) are allowed to co-propagate and interact. The original fluid model was set up for a non-magnetized plasma consisting of cold inertial ions evolving against a $$\kappa$$
κ
-distributed electron background in one dimension. The reduction procedure resulting in the CNLS equations has provided analytical expressions for the dispersion, self-modulation and cross-coupling coefficients in terms of the two carrier wavenumbers. These coefficients present no symmetry whatsoever, in the general case (of different wavenumbers). The possibility for coupled envelope (vector soliton) solutions to occur has been investigated. Although the CNLS equations are asymmetric and non-integrable, in principle, the system admits various types of vector soliton solutions, physically representing nonlinear, localized electrostatic plasma modes, whose areas of existence is calculated on the wavenumbers’ parameter plane. The possibility for either bright (B) or dark (D) type excitations for either of the (2) waves provides four (4) combinations for the envelope pair (BB, BD, DB, DD), if a set of explicit criteria is satisfied. Moreover, the soliton parameters (maximum amplitude, width) are also calculated for each type of vector soliton solution, in its respective area of existence. The dependence of the vector soliton characteristics on the (two) carrier wavenumbers and on the spectral index $$\kappa$$
κ
characterizing the electron distribution has been explored. In certain cases, the (envelope) amplitude of one component may exceed its counterpart (second amplitude) by a factor 2.5 or higher, indicating that extremely asymmetric waves may be formed due to modulational interactions among copropagating wavepackets. As $$\kappa$$
κ
decreases from large values, modulational instability occurs in larger areas of the parameter plane(s) and with higher growth rates. The distribution of different types of vector solitons on the parameter plane(s) also varies significantly with decreasing $$\kappa$$
κ
, and in fact dramatically for $$\kappa$$
κ
between 3 and 2. Deviation from the Maxwell-Boltzmann picture therefore seems to favor modulational instability as a precursor to the formation of bright (predominantly) type envelope excitations and freak waves.