Methods for forming multiphasic microparticles by using wettability engendered template self-assembly (WETS) techniques are provided. A template is used that defines wettable regions to polar and non-polar liquids and non-wettable regions to polar and non-polar liquids. A first liquid is applied to the template and forms a solid or semi-solid release layer. A second liquid is applied over the release layer to form a solid or semi-solid first layer and a third liquid is applied over the first layer to form a solid or semi-solid second layer. The first layer and the second layer can be released from the template by removing the release layer from the template with a treatment agent to form multiphasic microparticles. Methods for making the templates and multiphasic microparticles are also provided.