Two classes (type A and type B) of novel photolabile divinyl functionalized crosslinkers based on o-nitrobenzyl derivatives were synthesized and investigated with regard to their photolytic performance upon UV irradiation. The systematic variation of the molecular structure resulted in different degradation rates depending on the irradiation conditions. Thus, the successive and independent cleavage is enabled by either adjusting the applied wavelengths or irradiation times. The respective molecules were used to build up photodegradable PMMA microgels by free radical copolymerization with MMA in a miniemulsion polymerization process. UV light-induced degradation of the swollen microgels was monitored by time dependent turbidity measurements and the resulting kinetics were found to correlate with the photolysis rates of the respective crosslinkers in solution. The irradiation wavelength-controlled selective partial cleavage of type B crosslinking points was achieved by UV irradiation with λ > 315 nm and resulted in particles with extensively increased volumes consisting of highly swollen networks. In addition, the irradiation time-controlled selective complete degradation of particles containing type B crosslinkers was accomplished. By using broadband UV light containing wavelengths of λ < 315 nm, the successive complete particle disintegration of type B and type A microgels was observed. Hence, the specific performance of the synthesized microgels can be precisely triggered by means of the used UV light wavelengths, doses and intensities, thus representing a great potential as new light-responsive nanoscaled materials.