© 2020 SPIE. Organic-inorganic hybrid polymers based on ureasils have found application as waveguides in luminescent solar concentrators and visible light communications. The mechanical properties, and thus processability of ureasils, has previously been qualitatively linked to the chemical structure, but has not yet been studied in detail. In this study, a series of low molecular weight ureasil polymers has been synthesised, and the correlation between the chemical structure and the optical and mechanical properties investigated. A wide-range of techniques are employed to investigate this relationship, including steady-state photoluminescence and Fourier-transform infrared spectroscopy, 4-point flexural testing, and uniaxial tensile testing.