No. Only MonoDevelop can be used as a line-by-line debugger in Unity 3. MonoDevelop is a .NET-like environment for Windows and OSX.
There is a very high-effort way to get this working, as the wire-protocol that MonoDevelop uses to communicate with the builtin debugger inside Unity is "documented" as the sourcecode that writes/reads to it is opensource. It would be possible to write a Visual Studio plugin that talks Unity in the "debugger language" it understands. This is defenitely not a light undertaking however. (for implementation, see Mono.Debugger.Soft.dll in mono's sourcecode)
In short, once you have Visual Studio and Unity Tools https://www.visualstudio.com/en-us/features/unitytools-vs.aspx you can launch your game, open your code in Visual Studio (double-click on a script if Visual Studio is configured to be your code editor) and then click on the “Attach to Unity” button.
with the mono tools and a modified version / adopted version of the u3 monodevelop plugin it could work.
but the mono tools for vs are a heck expensive so actually using monodevelop and report the bugs so it can be pushed forward has a much stronger longterm benefit
You have to debug using the MonoDevelop that ships with Unity 3.2.
When you have the project open in MD, click Run > Attach to Process. Then choose the Unity editor process or your running built debug exe. If you attach to the editor, you can start and stop the game editor at any time using the "play" button or Ctrl+P.