Ultrafine particles (UFPs) with diameters smaller than 100 nm are omnipresent in ambient air. They are important sources for fine particles produced through the agglomeration and/or vapor condensation. With their unique properties, UFPs have also been manufactured for industrial applications. But, from the toxicological and health perspective, ultrafine particles with high surface-to-volume ratios often have high bio-availability and toxicity. Many recent epidemiologic studies have evidence UFPs are highly relevant to human health and disease. In order to better investigate UFPs, better instrumentation and measurement techniques for UFPs are thus in need. The overall objective of this dissertation is to advance out current knowledge on UFPs generation and measurement. Accordingly, it has two major parts: (1) ultrafine particle generation for laboratory aerosol research via electrospray (ES), and (2) ultrafine particle measurement for ambient aerosol monitor and personal exposure study via the development of a cost-effective and compact electrical mobility particle sizer. In the first part, to provide monodisperse nanoparticles, a new single capillary electrospray with a soft X-ray photoionizer as a charge reduction scheme has been developed. The soft X-ray effects on electrospray operation, particle size distribution and particle charge reduction were evaluated. To generate ultrafine particles with sufficient mass concentration for exposure/toxicity study, a TSE twin-head electrospray (THES) was evaluated, as well. The configuration and operational variables of the studied THES has been optimized. Three different nanoparticle suspensions were sprayed to investigate material difference. In the second part, to develop a miniature electrical mobility based ultrafine particle sizer (mini e-UPS), a new mini-plate aerosol charger and a new mini-plate differential mobility analyzer (DMA) have been developed. The performances of mini-plate charger and mini-plate DMA were carefully evaluated for ultrafine particles, including intrinsic/extrinsic charging, extrinsic charge distribution, DMA sizing accuracy and DMA transfer function. A prototype mini e-UPS was then assembled and tested by laboratory generated aerosol. Also a constrained least square method was applied to recover the particle size distribution from the current measured by a mini Faraday Cage aerosol electrometer.