Photosensitive glasses for radiation-induced 3D microstructuring, due to their optical transparency and thermal, mechanical, and chemical resistance, enable the use of new strategies for numerous microscale applications, ranging from optics to biomedical systems. In this context, we investigated the plasma etching of photosensitive glasses after their exposure and compared it to the established wet chemical etching method, which offers new degrees of freedom in microstructuring control and microsystem fabrication. A CF4/H2 etching gas mixture with a constant volumetric flow of 30 sccm and a variable H2 concentration from 0% to 40% was utilized for plasma-based etching, while for wet chemical etching, diluted hydrofluoric acid (1% ≤ cHF ≤ 20%) was used. Therefore, both etching processes are based on a chemical etching attack involving fluorine ions. A key result is the observed reversion of the etch selectivity between the initial glassy and partially crystallized parts that evolve after UV exposure and thermal treatment. The crystallized parts were found to be 27 times more soluble than the unexposed glass parts during wet chemical etching. During the plasma etching process, the glassy components dissolve approximately 2.5 times faster than the partially crystalline components. Unlike wet chemical etching, the surfaces of plasma etched photostructured samples showed cone- and truncated-cone-shaped topographies, which supposedly resulted from self-masking effects during plasma etching, as well as a distinct physical contribution from the plasma etching process. The influences of various water species on the etching behaviors of the homogeneous glass and partially crystallized material are discussed based on FTIR-ATR and in relation to the respective etch rates and SNMS measurements.