Key Message: This article presents the enhancement in boron fixation as well as the improved biological resistance against fungi and termites for wood samples treated with tannin-caprolactam and tannin-PEG formulations. Context: Although the recently developed tannin-boron wood preservatives have shown high biological protection, they presented also average resistance against weathering. The tannin-caprolactam formulations have shown improved weathering resistances and dimensional stability. Aims: For this reason, more detailed biological tests were performed to evaluate the influence of the caprolactam and PEG on the biological resistance. Methods: In this paper, the boron leaching of the tannin-caprolactam and tannin-PEG impregnated Scots pine specimens was observed and the biocidal effect against fungi (Antrodia spp. and Coniophora puteana) and insects (Reticulitermes flavipes and Hylotrupes bajulus) were determined according to the guidelines of EN 113, EN 117, and EN 47. Results: The advanced formulations containing PEG have shown interesting resistance against fungal decay, but very low penetration and weak resistance against larvae while the tannin-caprolactam preservatives have shown overall improved biological performances and higher boron fixations. Conclusion: The biocidal activity of the caprolactam-added formulations was overall enhanced and therefore these formulations are confirmed to be an interesting alternative for the wood preservation in outdoor environment. (Résumé d'auteur)