We report the discovery of a hot white dwarf (WD) companion to a blue straggler star (BSS) in the globular cluster (GC) NGC 5466, based on observations from the Ultra-Violet Imaging Telescope (UVIT) on board AstroSat. The Spectral Energy Distribution (SED) of the Far-UV detected BSS NH 84 was constructed by combining the flux measurements from 4 filters of UVIT, with GALEX, GAIA and other ground-based observations. The SED of NH 84 reveals the presence of a hot companion to the BSS. The temperature and radius of the BSS (T$_{mathrm{eff}} = 8000^{+1000}_{-250}$ K, R/R$_odot = 1.44 pm 0.05$) derived from Gemini spectra and SED fitting using Kurucz atmospheric models are consistent with each other. The temperature and radius of the hotter companion of NH 84 (T$_{mathrm{eff}} = 32,000 pm 2000$ K, R/R$_odot = 0.021 pm 0.007$) derived by fitting Koester WD models to the SED suggest that it is likely to be a hot WD. The radial velocity derived from the spectra along with the proper motion from GAIA DR2 confirms NH 84 to be a kinematic member of the cluster. This is the second detection of a BSS-WD candidate in a GC, and the first in the outskirts of a low density GC. The location of this BSS in NGC 5466 along with its dynamical age supports the mass-transfer pathway for BSS formation in low density environments.