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Printer characterization usually requires many printer inputs and corresponding color measurements of the printed outputs. In this brief, a sampling optimization for printer characterization on the basis of direct search is proposed to maintain high color accuracy with a reduction in the number of characterization samples required. The proposed method is able to match a given level of color accuracy requiring, on average, a characterization set cardinality which is almost one-fourth of that required by the uniform sampling, while the best method in the state of the art needs almost one-third. The number of characterization samples required can be further reduced if the proposed algorithm is coupled with a sequential optimization method that refines the sample values in the device-independent color space. The proposed sampling optimization method is extended to deal with multiple substrates simultaneously, giving statistically better colorimetric accuracy (at the α = 0.05 significance level) than sampling optimization techniques in the state of the art optimized for each individual substrate, thus allowing use of a single set of characterization samples for multiple substrates.