Carrier relaxation processes have been investigated in GaAs/AlGaAs v-groove quantum wires (QWRs) with a large subband separation (46 meV). Signatures of inhibited carrier relaxation mechanisms are seen in temperature-dependent photoluminescence (PL) and photoluminescence-excitation (PLE) measurements; we observe strong emission from the first excited state of the QWR below ~50 K. This is attributed to reduced inter-subband relaxation via phonon scattering between localized states. Theoretical calculations and experimental results indicate that the pinch-off regions, which provide additional two-dimensional confinement for the QWR structure, have a blocking effect on relaxation mechanisms for certain structures within the v-groove. Time-resolved PL measurements show that efficient carrier relaxation from excited QWR states into the ground state, occurs only at temperatures > 30 K. Values for the low temperature radiative lifetimes of the ground- and first excited-state excitons have been obtained (340 ps and 160 ps respectively), and their corresponding localization lengths along the wire estimated.