In this work, we investigated the activity of Keggin heteropolyacid catalysts (i.e., H3PW12O40, H3PMo12O40 and H4SiW12O40) in beta-pinene reactions with alkyl alcohols (i.e. methyl, ethyl, propyl, sec-propyl, butyl and sec-butyl alcohols), and exploring the different aspects that drive the selectivity of this process. We have found that carbon skeletal rearrangements and isomerization providing intermediate carbocations that controlling the reaction selectivity. beta-pinene was preferentially converted to alpha-terpinyl ion which undergoes a nucleophilic attack of alcohol providing alkyl alcohol. Bornyl ion was converted to bornyl and fenchyl ethers. The other secondary products were beta-pinene isomers obtained from bornyl and alpha-terpinyl carbocations. Phosphotungstic acid (i.e., H3PW12O40) was the most active catalyst and selective toward the main product (alpha-terpinyl alkyl ether); the highest conversion (ca. 96%) and ether selectivity (ca. 61%) was achieved in the reactions with beta-pinene. Although having also been alkoxylate, alpha-pinene was less reactive (ca. 40%), while camphene and limonene remained unreactive under reaction conditions studied. An increase of temperature resulted in an improvement on conversion of beta-pinene and selectivity toward alpha-terpinyl methyl ether. Similarly, the H3PW12O40 concentration played a crucial role on reaction selectivity. This work presents positive features such as a short reaction time, high atom economy, mild reaction conditions (i.e., low temperature and room pressure). Even though soluble the catalyst was easily recovered by liquid -liquid extraction and efficiently reused. [GRAPHICS] .