We report the discovery with the Neutron Star Interior Composition Explorer (NICER) of narrow emission and absorption lines during photospheric radius expansion (PRE) X-ray bursts from the ultracompact binary 4U 1820−30. NICER observed 4U 1820−30 in 2017 August during a low flux, hard spectral state, accumulating about 60 ks of exposure. Five thermonuclear X-ray bursts were detected of which four showed clear signs of PRE. We extracted spectra during the PRE phases and fit each to a model that includes a comptonized component to describe the accretion-driven emission, and a black body for the burst thermal radiation. The temperature and spherical emitting radius of the fitted black body are used to assess the strength of PRE in each burst. The two strongest PRE bursts (burst pair 1) had black body temperatures of ≈ 0.6 keV and emitting radii of ≈ 100 km (at a distance * NASA Postdoctoral Fellow Cottam,