Eight bromine, cyano- and carbonyl- electron withdrawing group containing glassy derivatives of azobenzene with incorporated bulky triphenyl moieties through several chemical design approaches have been synthesized and investigated. The attachment of such bulky groups to the azobenzene chromophore through ether bonds leads to the highest diffraction efficiencies (up to 57%) and the highest glass transitions (up to 106 oC), incorporation through ester bonds as well as additional azo-group insertion enhances photosensitivity (Wmax up to 3.7 J/(cm2%)) and thermal stability (up to 312 oC), while bonding through methylene linkers make it possible to conduct holographic recording with 633 nm laser (self-diffraction efficiency up to 15%). The design of amorphous azodyes with bulky triphenyl moieties as well as free hydroxyl-groups increase diffraction efficiencies in the case of L-R polarization and photosensitivity in the case of p-p polarization in relation to azocompounds with incorporated triphenyl groups only. High surface relief grating (SRG) depths reaching 1100 nm and in several cases even exceeding the thickness of the films were found. Synthesized glassy azodyes show potential for holographic recording applications, while the designed approach could be utilized in preparation of different materials suitable not only for holographic recording but also in other emerging fields of photonics.