VAX's predecessor, the PDP-11, is also a little-endian architecture in its basic form (and the PDP-11 was also a major source of influence to many microprocessor designers, just like VAX's influence on Unix workstations).
The "PDP-endian" is only a quirk due to its Floating Point Unit's long integer and double-precision floating point formats. The FPU was an extra module attached to the processor, and the original PDP-11 did not even have an FPU. It only appeared on later models: on low-end machines a simplified FPU version was available for separate purchase with limited functionalities, and only high-end models had the full FPU. On a system without FPU installed, you basically don't need to worry about "PDP-endian", it's a pure little-endian machine. But for convenience, the Unix C compiler always stored long integers in PDP-endian to avoid swapping endians. Because the same Unix and C software ran on all machines with or without FPU, all Unix programmers needed to worry about it, thus the PDP-endian folklore.
But why did the PDP-11 FPU use this strange format? @aka_pugs from Twitter did some digging, and found the PDP-endian was already in used as a softfloat format by DEC's PDP-11 Fortran compiler. So the FPU was made compatible with that...
PDP-11 long ints were mixed- endian: high 16 bits, then low 16 bits. But within each half, the low 8 bits, then upper 8 bits. I was sometimes called the "NUXI" format, for how it scrambled the bytes in "UNIX".
What I was saying is that the basic PDP-11 as original designed, is a pure 16-bit machine with no 32-bit capabilities. The Unix C and other compilers used the middle-endian format for 32-bit integers largely as an artificial choice to be compatible with its FPU, as middle-endian was FPU's native long integer format. But the FPU was only a later hardware extension, and was not an inherent part of the basic system, and it's not enforced by the basic PDP-11 insturction set. It's entirely possible to modify the UNIX C compiler to store long integers in little endian.
The "PDP-endian" is only a quirk due to its Floating Point Unit's long integer and double-precision floating point formats. The FPU was an extra module attached to the processor, and the original PDP-11 did not even have an FPU. It only appeared on later models: on low-end machines a simplified FPU version was available for separate purchase with limited functionalities, and only high-end models had the full FPU. On a system without FPU installed, you basically don't need to worry about "PDP-endian", it's a pure little-endian machine. But for convenience, the Unix C compiler always stored long integers in PDP-endian to avoid swapping endians. Because the same Unix and C software ran on all machines with or without FPU, all Unix programmers needed to worry about it, thus the PDP-endian folklore.
But why did the PDP-11 FPU use this strange format? @aka_pugs from Twitter did some digging, and found the PDP-endian was already in used as a softfloat format by DEC's PDP-11 Fortran compiler. So the FPU was made compatible with that...