Organoselenium compounds find broad applications across numerous fields. The synergistic combination of polyfluoroaromatic rings with organoselenium moieties generates unique molecular architectures with properties valuable for supramolecular chemistry, medicine, materials science, and organic synthesis. We report the first versatile one-pot methodology enabling direct conversion of readily available pentafluorobenzenes into three distinct classes of polyfluorinated organoselenium compounds using Na2Se as the selenium source. The approach proceeds via a key ArFSeNa intermediate that can be selectively transformed under controlled conditions. Symmetrical selenides are obtained in yields of up to 79% across 17 substrates under the optimized conditions (DMF, 130 °C, 3 h), while diselenides are accessible under considerably milder conditions (50 °C, 10 min) with yields reaching 92% for 18 examples. Remarkably, unsymmetrical selenides can be prepared at ambient temperature within 10 min, affording 14 products in yields of up to 90%. The method shows excellent functional group tolerance and regioselectivity, with substitution occurring preferentially at the para-position relative to substituents on the perfluorinated ring. This methodology represents a paradigm shift in organoselenium chemistry by eliminating the need for hazardous intermediates, reducing synthetic complexity from multistep sequences to single operations, and operating under significantly milder conditions