The present paper gives a deeper insight into the chain ordering in aqueous polyelectrolyte solutions under geometrical confinement as a function of degree of polymerization and polymer concentration. Colloidal probe atomic force microscopy (CP-AFM) and small-angle X-ray scattering (SAXS) are used to compare the poly(styrenesulfonate) (NaPSS) chain ordering between two solid interfaces and in bulk, respectively. Oscillatory force-distance curves from CP-AFM as well as the scattering peaks from SAXS indicate a near range ordering of polyelectrolyte chains with structural parameters such as interchain distance, correlation length, and the strength of ordering. These characteristic lengths from CP-AFM (confinement) and SAXS (bulk) are in the same range. The interchain distance is up to 20% smaller and the correlation length is up to 20% higher under confinement, indicating a slight compression of the polyelectrolyte chains and a stronger counterion condensation under confinement. The interchain distance d scales with the monomer unit concentration c as d similar to c(-1/3) for a degree of polymerization N from 20 to 155 and as d similar to c(-1/2) for N = 367 and 10690, indicating a dilute and semidilute regime, respectively. The transition from dilute to semidilute regime is in good agreement with the one found in viscosity measurements and with theoretical concepts. At a fixed monomer concentration, d depends on the chain length in the dilute regime while it is independent of the molecular weight in the semidilute regime. The experimental intercoil distance d in the dilute regime coincides well with the one calculated from the coil number density, which is based in turn on a theoretical model. Other models for calculating the interchain distance are discussed. The correlation length of the ordering increases with increasing molecular weight, indicating an increase in counterion condensation. The strength of ordering increases with the degree of polymerization due to entropic reasons.