Wetting behavior of fluid/fluid/solid systems, largely influenced by surface properties and interactions between the three phases, plays a big role in nature and in industrial applications Traditionally, wetting studies have focused on liquid/vapor systems, especially the study of a sessile liquid droplet in air. Liquid/vapor systems can only probe the effects of surface properties and interactions between the solid and the wetting liquid. This type of characterization is inadequate for liquid/liquid systems, where surface wettability is additionally influenced by interactions between the two wetting liquids. The present study is the first to examine the effects of nanoscale roughness on wetting behavior in liquid/liquid systems and the modulation of roughness effects by fluid properties and the wetting order. This study examines both equilibrium and dynamic wetting behavior in liquid/liquid systems using well characterized substrates. Rough substrates were fabricated by coating glass substrates with nanometer sized polymer particles. Partial dissolution of the particles and molecular de-deposition of the polymer allowed for tuning of substrate roughness while retaining the original surface chemistry. The effectiveness of this fabrication technique was verified using electron microscopy and electrokinetic analysis. We examined the wetting behavior in three fluid/fluid systems: an air/water system, a decane/water system, and an octanol/water system. The oils were chosen based on their different polarities. Equilibrium wetting behavior was determined using contact angle measurements. Results indicate that for all systems where the primary wetting fluid was a liquid, an increase of the surface roughness resulted in Cassie-Baxter wetting. How hydrophilic a surface appears with regard to a water/fluid interface depended on the polarity of that fluid. The octanol/water system provided the strongest evidence regarding the effect of wetting order: a transition from Wenzel to Cassie-Baxter wetting was only observed when water was the primary wetting liquid. The observed transition was confirmed using a modified Wenzel/Cassie-Baxter model. The kinetics of droplet spreading was measured using high speed optical microscopy. After a droplet was placed on a solid surface, the motion of the contact line was imaged at a rate of 1000 fps. The wetted area was then extracted using custom Matlab® scripts. The spreading kinetics underwent a transition between two regimes: a visco-inertial regime and a slower spreading regime. Results indicated that surface roughness influenced spreading kinetics in both regimes. The overall spreading rate was always slower for rough surfaces than for smoother surfaces. In liquid/liquid systems, the duration of visco-inertial regime was dependent on the surface roughness as well; in general, it was shorter for smooth substrates compared to rough substrates. Increasing the viscosity of the non-aqueous fluid significantly increased the duration of the visco-inertial regime and decreased the overall spreading rate. This study provides insight into the competitive wetting of solid surfaces relevant in many industrial applications such as oil recovery or inkjet printing, and may guide the development of improved wetting models in an area that currently lacks an adequate theoretical description.