Firstly, two new cellulose derivatives (CelB33′44′TD and Cel44′OA) were synthesized, which were confirmed by FTIR and 13C CP-MAS NMR spectra. These derivatives were then used in the construction of new diodes (Au/CelB33′44′TD/p-Si and Au/Cel44′OA/p-Si). Later, the atomic force microscope (AFM) images of the interface layers were taken, and the current–voltage (I–V) graphs of the diodes were determined both in the dark and under different illumination intensities (DIIs). Using the Bethe's thermionic emission (TE) theory the ideality factors and barrier heights of the diodes, using the Cheung & Cheung functions the ideality factors, series resistances and barrier heights of the diodes, and using the Norde function the barrier heights and series resistances of the diodes were calculated. Finally, the capacitance–voltage (C–V) and conductance–voltage (G–V) graphs of the diodes at different frequencies (DFs) were examined and some frequency-dependent electrical parameters of the diodes were calculated using the 1/C2–V plots.