The spectroscopic and electronic properties of small-molecular organic semiconductors in thin films are a significant aspect that controls the performance of their optical/optoelectronic devices. A heterojunction of thermal vacuum deposited film of tin(II)2,3-naphthalocyanine (SnNC) dye onto a p-type Si wafer (SnNC/p-Si) was fabricated. The morphology of SnNC thin film onto Si wafer was explored using the Field Emission Scanning Electron Microscope (FE-SEM). The specular reflectance and the fluorescent properties of SnNC thin film onto Si wafer were investigated. The PL emission spectra of SnNC/p-Si emission bands are related to the B and Q absorption bands for SnNC. The spectral behavior of the refractive index and the specific polarizability for both SnNC/Glass and SnNC/p-Si were extracted. Under varying temperatures (298–378 K), the electronic properties of the SnNC/p-Si heterojunction were analyzed in dark conditions. The diode parameters of SnNC/p-Si heterojunctions were extracted from the current-voltage (I-V) procedure, which exhibited temperature-dependent behavior. According to the Cheung-Cheung and Norde procedure, the essential electrical diode parameters of the SnNC/p-Si device such as the ideality factor, the series resistance, and barrier height were estimated. The photoconductivity parameters such as the photocurrent, the sensitivity, and the responsivity of the SnNC/p-Si devices were estimated. We believe that these findings can be useful and utilized in optoelectronic and organic electronic applications.