Chemical composition analysis using sampling practices in as-cast aluminum alloys are not accurate enough. Optical emission spectrometry (OES) analyses of samples taken at specified milling depths do not match the desired nominal composition due to segregation phenomenon. Moreover, macrosegregation profiles within samples cast with current molds often exhibit significant variations. Various types of molds have been tested in the past to solve this problem, but none have had a satisfactory outcome. This paper presents research on a novel mold with an insulated periphery designed to yield more accurate sampling tests. The results from samples made with the insulated periphery mold show segregation profiles with good reproducibility. A value close to the nominal composition was observed at 6–7 mm milling depth. The reproducibility of segregation profiles is correlated to one-dimensional solidification, minimizing surface segregation areas, and melt convection.