In this work, we report on the synthesis of a new-age reusable visible-light photocatalyst using a heterojunction nanocomposite of W⁶⁺/Yb³⁺ on a mixed-phase mesoporous network of monolithic TiO₂. The structural properties of the monolithic photocatalysts are characterized using p-XRD, SEM-EDAX, TEM-SAED, XPS, PLS, UV–Vis-DRS, FT-IR, micro-Raman, TG–DTA, and N₂ isotherm analysis. The electron microscopic analysis reveals a mesoporous network of ordered worm-like monolithic design, with a polycrystalline mixed-phase (anatase/rutile) TiO₂ composite, as indicated by diffraction studies. The UV–Vis-DRS analysis reveals a redshift in the light absorption characteristics of the mixed-phase TiO₂ monolith as a function of W⁶⁺/Yb³⁺ co-doping. It is observed that the use of (8.0 mol%)W⁶⁺/0.4 (mole%)Yb³⁺ co-doped monolithic TiO₂ photocatalyst, with an energy bandgap of 2.77 eV demonstrates superior visible-light photocatalysis, which corroborates with the PLS studies in terms of voluminous e⁻/h⁺ pair formation. The practical application of the photocatalyst has been investigated through a time-dependent dissipation of enrofloxacin, a widely employed antimicrobial drug, and its degradation pathway has been monitored by LC–MS-ESI and TOC analysis. The impact of physio-chemical parameters such as solution pH, sensitizers, drug concentration, dopant/codopant stoichiometry, catalyst quantity, and light intensity has been comprehensively studied to monitor the process efficiency.