A novel calibration independent technique that simultaneously determines the optical constants and material thickness with high accuracy, using the transmission and the reflection measurements, is proposed. A generalized closed form expression is derived to calculate the optical constants in terms of the measured transmitted and the reflected signals. The proposed measurement technique is noniterative, self-calibrated, and independent of prior knowledge of the sample thickness. To validate the proposed technique, two different samples, viz., Gallium arsenide and Silicon, are considered during the numerical simulation. The result shows that the proposed technique provides highly accurate material parameters over a broad frequency domain and also recovers the information of the material thickness.