Two critical nanoscale design parameters (CNDPs); namely, surface chemistry and interior compositions of poly(amidoamine) (PAMAM) dendrimers were systematically engineered to produce unique hyperpolarizable, electro-optical substrates. These electro-optically active dendritic films were demonstrated to produce high quality, continuous wave terahertz radiation when exposed to a suitable pump laser that could be used for spectrometry and molecular imaging. These dendrimer based dipole excitation (DDE) terahertz sources were used to construct a working spectrometer suitable for many practical applications including THz imaging and analysis of encapsulated hydrogen species in fullerenes.