Endianness basically refers to the ordering of the bytes within words or larger bytes of data treated as a single entity.
When we consider a several bytes of data say for instance 4 bytes of data,XYZQ the lower byte if stored in a Higher address and others in successively decreasing addresses ,then it refers to the Big Endian and the vice versa of this refers to Little Endian architecture.
Intel 80x86 usually follows Little Endian and others like IBM systems follow Big Endian formats.
If the data is being transmitted care has to be taken so as to know as to which byte,whether the higher or the lower byte is being transmitted.
Hence a common format prior to communication has to be agreed upon to avoid wrong interpretation/calculations.
Usually layer modules are written so as to automate these conversion in Operating systems.