SCOPE: Silicon (Si) is an abundant element on earth. It is found naturally in water in the form of orthosilicic acid (OSA), however this form is not stable under certain conditions such as in highly concentrated and non‐neutral pH solutions, which lead to its polymerization and reduced bioavailability. This study aimed to assess the bioavailability of Si from OSA stabilized by vanillin (OSA‐VC). METHODS AND RESULTS: This was a single‐center, double‐blind, cross‐over randomized controlled trial. Fourteen healthy subjects were recruited and consumed either OSA‐VC or a placebo on two separate occasions. Blood and urine samples were collected during 6 h following ingestion and analyzed to determine Si absorption and excretion. Plasma Si area under the curve (0–6 h) was significantly higher after OSA‐VC ingestion compared to placebo ingestion (p = 0.0002). Significantly higher urinary Si excretion was also reported over the 6‐h period after OSA‐VC ingestion compared to placebo (p<0.0001). Approximately 21% of ingested Si was excreted in urine during this period. CONCLUSION: Although many studies have investigated the metabolism and bioavailability of Si supplemented in foods or as a food ingredient, this was the first to investigate and demonstrate the digestibility of OSA administered in a complex form with vanillin.