Over the past few decades, photocatalytic C–H functionalization reactions have received increasing attention due to the often mild reaction conditions and complementary selectivities to conventional functionalization processes. Now, photocatalytic C–H functionalization is a widely employed tool, supporting activities ranging from complex molecule synthesis to late-stage structure–activity relationship studies. In this perspective, we will discuss our efforts in developing a photocatalytic decatungstate catalyzed C–H fluorination reaction as well as its practical application realized through collaborations with industry partners at Hoffmann–La Roche and Merck, and extension to radiofluorination with radiopharmaceutical chemists and imaging experts at TRIUMF and the BC Cancer Agency. Importantly, we feel that our efforts address a question of utility posed by Professor Tobias Ritter in “Late-Stage Fluorination: Fancy Novelty or Useful Tool?” (ACIE, 2015, 54, 3216). In addition, we will discuss decatungstate catalyzed C–H fluoroalkylation and the interesting electrostatic effects observed in decatungstate-catalyzed C–H functionalization. We hope this perspective will inspire other researchers to explore the use of decatungstate for the purposes of photocatalytic C–H functionalization and further advance the exploitation of electrostatic effects for both rate acceleration and directing effects in these reactions.