N-tier architecture usually has each layer separated by the network. I.E. the presentation layer is on some web servers, then that talks to backend app servers over the network for business logic, then that talks to a database server, again over the network, and maybe the app server also calls out to some remote services (say Authorize.net for payment processing).
MVC is a programming design pattern where different portions of code are responsible for representing the Model, View, and controller in some application. These two things are related because, for instance the Model layer may have an internal implementation that calls a database for storing and retrieving data. The controller may reside on the webserver, and remotely call appservers to retrieve data. MVC abstracts away the details of how the architecture of an app is implemented.
N-tier just refers to the physical structure of an implementation. These two are sometimes confused because an MVC design is often implemented using an N-tier architecture.
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