Applications of molecular photoswitches in materials are of high interest because multiple properties can be controlled with nanoscale precision by simple outside light irradiation stimuli. Consequentially, the resulting light-responsive materials give rise to smart and programmable behavior, the potential of which is just starting to be tapped. A very potent yet simple approach in this regard is implementation of photoswitches into transparent polymers, endowing the latter with photochromism. This allows for reversible inscription of information with light and resulting applicability in optical memories, kryptographics, displays, or programmable filters. When geometrical or electronic changes of the molecular photoswitches are leading to corresponding changes within the embedding material, lightcontrol over its shape, density, aggregation state, or wettability (to name a few options) can be achieved. There are virtually limitless applications that result in such cases including soft robotics, haptic topological material changes, or self-healing. Photoswitches can further be used as molecular photoinitiators for polymerization and thus open up applications in 3D-printing, for 4D materials with dynamically controllable changes, or for sequence-precise information polymers (again to just name a few). In the overwhelming cases most common photoswitches are used for materials application, i.e. azobenzenes, diarylethenes, spiropyranes, or stilbenes. The latter are interesting for materials application in their own right in the more elaborate form of molecular machines. In this work we explore two very recent additions to the realm of photoswitches, hemiindigo (HI) (derivatives 1-8, Figure ) and aza-diarylethene 9 (Figure ), for their potential in advanced light-responsive materials. HIs belong to the emerging class of indigoid photoswitches, which show excellent switching properties, high thermal stability, and broadly tunable absorptions in the visible, red, and near infrared part of the electromagnetic spectrum. Aza-diarylethene 9 is a heterocyclic variant of diarylethenes and allows to reversibly form a CN double bond photochemically under zwitterion formation and aromatization. We now scrutinized a variety of different applications, starting with photochromic polymers (Figure ) and 3D-reversible relief photoimprinting (Figure ) before turning to light-induced radical polymerization initiation (Figure ), using the resulting polymers to generate photochromic polymers by addition of compounds 1-7, and 9 (Figure ), and finally synergizing photocontrolled polymerization and localized photochromism simultaneously (Figure ).