Today, a lot of attention is paid to remote controlled opto-electronic devices. Many of them are commonly used in the society, industry, and science. Accessories dedicated to the particular utilization are desired. The point is to find a simple way to obtain smart and functional appliances. Materials engineering faces such problems and provides a variety of solutions concerning advanced material design, preparation, and utilization. Photochromic materials represent one of the already known materials, which still find other objectives in new fields of life. In our work, we present two differently constructed photoresponsive polymers, which give significantly different nonlinear optical (NLO) response visible as noticeable optical signal modulation. By playing with diversified laser light energy or its frequency, NLO output characterized appealing, and individual characteristics (doubled Δn ∼0.02 vs 0.04 and entirely different kinetics for two similar materials and the same laser pumping). Interestingly, high output signal repeatability and stability were achieved, which indicate the investigated materials as promising candidates in the construction of various opto-electronic devices. Additionally, a set of photoresponsive studies, reflectometry, and theoretical insights was performed and included in this work.