β<sub>2</sub>-Adrenoceptors (β<sub>2</sub>-AR) are prototypical G-protein-coupled receptors and important pharmacological targets with relevant roles in physiological processes and diseases. Herein, we introduce <b>Photoazolol-1-3</b>, a series of photoswitchable azobenzene β<sub>2</sub>-AR antagonists that can be reversibly controlled with light. These new photochromic ligands are designed following the azologization strategy, with a <i>p</i>-acetamido azobenzene substituting the hydrophobic moiety present in many β<sub>2</sub>-AR antagonists. Using a fluorescence resonance energy transfer (FRET) biosensor-based assay, a variety of photopharmacological properties are identified. Two of the light-regulated molecules show potent β<sub>2</sub>-AR antagonism and enable a reversible and dynamic control of cellular receptor activity with light. Their photopharmacological properties are opposite, with <b>Photoazolol-1</b> being more active in the dark and <b>Photoazolol-2</b> demonstrating higher antagonism upon illumination. In addition, we provide a molecular rationale for the interaction of the different photoisomers with the receptor. Overall, we present innovative tools and a proof of concept for the precise control of β<sub>2</sub>-AR by means of light.