In this work, we introduce a simple solvent-assisted micromolding technique for the fabrication of high-fidelity styrene-ethylene/butylene-styrene (SEBS) microfluidic devices with high polystyrene (PS) content (42 wt% PS, SEBS42). SEBS triblock copolymers are styrenic thermoplastic elastomers that exhibit both glassy thermoplastic and elastomeric properties resulting from their respective hard PS and rubbery ethylene/butylene segments. The PS fraction gives SEBS microdevices many of the appealing properties of pure PS devices, while the elastomeric properties simplify fabrication of the devices, similar to PDMS. SEBS42 devices have wettable, stable surfaces (both contact angle and zeta potential) that support cell attachment and proliferation consistent with tissue culture dish substrates, do not adsorb hydrophobic molecules, and have high bond strength to wide range of substrates (glass, PS, SEBS). Furthermore, SEBS42 devices are mechanically robust, thermally stable, as well as exhibit low auto-fluorescence and high transmissivity. We characterize SEBS42 surface properties by contact angle measurements, cell culture studies, zeta potential measurements, and the adsorption of hydrophobic molecules. The PS surface composition of SEBS microdevices cast on different substrates is determined by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The attractive SEBS42 material properties, coupled with the simple fabrication method, make SEBS42 a quality substrate for microfluidic applications where the properties of PS are desired but the ease of PDMS micromolding is favoured.