Electronic absorption spectra of 2,7,12,17-tetra-tert-butylporphycene (TTPC) have been recorded in low-temperature argon and xenon matrices for various deposition conditions. In the region of the S(0)-S(1) electronic transition, the spectra of TTPC in argon reveal a rich site structure, characterized by a series of more than 30 absorption peaks. Studies of the temperature dependence of the electronic spectra in solid argon demonstrated remarkable spectral changes, resulting in the broadening of all bands with increasing temperature. These temperature-induced spectral changes are, to a large degree, reversible, so lowering of temperature is accompanied by the recovery of the original fine-line spectrum. The absorption spectra in xenon reveal broad bands, on which a rich pattern of lines becomes superimposed at low temperatures. Trapping site distribution and the structure of the microenvironment around the TTPC chromophore, embedded in argon and xenon hosts, have been analyzed using molecular dynamics (MD) simulations. The MD results show that the trapping of TTPC in rare-gas solids is influenced by favorable embedding of the bulky tert-butyl groups inside the matrix cage. The crucial role of the tert-butyl groups for the thermodynamics and kinetics of matrix deposition is demonstrated by comparing the results with those obtained for the parent, unsubstituted porphycene.