The X86 has always supported unaligned accesses. In the ARM world the first architecture that supported unaligned accesses in hardware was ARMv6. The architecture was implemented in the ARM11 core around the year 2002 and onward. There is an excellent article at ARM Infocenter giving technical details:

http://infocenter.arm.com/help/index.jsp?topic=/com.arm.doc.faqs/ka15414.html

The support for unaligned accesses must be enabled in an ARM core explicitly. This is done by setting the bit A in the register SCTLR. Still, unaligned accesses will be allowed only on Normal memory; accesses to  Device memory type are always checked and will throw exceptions on misaligned accesses.