Among biogenic volatile organic compounds (BVOCs) in the natural ecosystem, monoterpenes, along with isoprene, play important roles in atmospheric chemistry and make significant impacts on air pollution and climate change, especially due to their contribution to secondary organic aerosol production and photochemical ozone formation. It is essential to measure monoterpene concentrations accurately for understanding their oxidation processes, emission processes and estimation, and interactions between biosphere and atmosphere. Thus, traceable calibration standards are crucial for the accurate measurement of monoterpenes at ambient levels. However, there are limited information about developing calibrations standards for monoterpenes in pressured cylinders. This study describes about developing primary standard gas mixtures (PSMs) for monoterpenes at about 2 nmol/mol, near ambient levels. The micro-gravimetric method was applied to prepare monoterpene (α-pinene, 3-carene, R-(+)-limonene, 1,8-cineole) PSMs at 10 μmol/mol and then the PSMs were further diluted to 2 nmol/mol level. To select an optimal cylinder for the development of monoterpene PSMs, three different kinds of cylinders were used for the preparation and were evaluated for uncertainty sources including long-term stability. Results showed that aluminum cylinders with a special internal surface treatment (Experis) had little adsorption loss on the cylinder internal surface and good long-term stability compared to two other cylinder types with no treatment and a special treatment (Aculife). Results from uncertainty estimation suggested that monoterpene PSMs can be prepared in pressured cylinders with a special treatment (Experis) at 2 nmol/mol level with an uncertainty of less than 4%.