Adsorption is a widely applied technique in producing high-purity chemicals with advantages of low energy consumption, high selectivity, and mild operating conditions. However, traditional adsorbents have inflexible properties and suffer from the trade-off between selective adsorption and efficient desorption. Recently, the emerging photoresponsive adsorbents have provided new avenues for adsorption techniques. Active sites of photoresponsive adsorbents can be regulated through steric hindrance or tunable adsorbent-adsorbate interactions. Therefore, variation in adsorptive capacity is able to readily achieve through photomodulation, and the corresponding adsorption/desorption cycles are energy-saving. This concept mainly summarizes recent efforts on the fabrication and application of photoresponsive adsorbents with tunable active sites. Also, the future opportunities and critical challenges of photoregulation on adsorptive sites are presented.