Highly efficient and an environmentally benign method has been developed for the direct one-pot synthesis of beta-hydroxysulfides in good yields under mild and neutral conditions from alkenes and thiophenols in the presence of aerial oxygen using a mixture of ionic liquid [bmim][BF4] and water. This protocol tolerates a wide variety of functional groups or substrates and does not require the use of either acid or base catalysts. Ionic liquid can be recovered and reused for a number of runs with negligible loss of its activity. (c) 2007 Elsevier B.V. All rights reserved.