This chapter describes briefly chemical shifts (or nuclear magnetic shielding constants) and indirect spin–spin coupling constants. They are well known as powerful tools for studying several molecular properties which are very important in different branches of the broad field of molecular sciences. The present description is oriented to an interdisciplinary audience and therefore it is expected that it can be followed for readers without strong backgrounds either in mathematics or physics. After a short revision of basic concepts, a qualitative method devised to extract information on electronic molecular structures is described. This aim is achieved employing this qualitative method for relating such parameters known in different series of compounds with several common chemical interactions. Since both types of NMR parameters present second-rank tensor properties, it is discussed how such property is affected in molecules measured in isotropic phase. Anybody with mathematical and physical background would answer immediately, “in isotropic phase is only observed one-third of the respective tensor trace.” However, in molecules that trace depends on the relative orientation of the Principal Axes System and bonds associated to the atom whose nuclear magnetic shielding is studied, or to the straight line connecting a pair of coupled nuclei. To describe these effects in this chapter is coined the expression “the geometric effect” to identify them. The same expression is also employed in . A list of exercises and appropriate references are included at the end of this chapter.